Composite structures for packaging articles and related methods

ABSTRACT

The composite structure includes a fiber-containing layer, such as a fiberboard layer or other layer having fibers from natural and/or synthetic sources, and a mineral-containing layer covering the fiber-containing layer. The fiber-containing layer and mineral-containing layer can be shaped, sized and manufactured such that the composite structure formed therefrom is capable of being machined to form a storage article. The composite structure has advantages in that it can improve whiteness, opacity, ink adhesion, materials reduction, barrier properties, recyclability, and printability. The composite can reduce polymer mass requirements for heat seal, barrier, and fiber adhesion. Further improvements include economics, pliability, and flexibility that is increased over the pliability of the fiber-containing layer alone.

CROSS-REFERENCE TO RELATED APPLICATIONS

This Application is a continuation of U.S. patent application Ser. No.18/330,894, filed on Jun. 7, 2023, titled “COMPOSITE STRUCTURES FORPACKAGING ARTICLES AND RELATED METHODS”, the contents of which areexpressly incorporated herein by this reference, and to which priorityis claimed. U.S. patent application Ser. No. 18/330,894 is acontinuation of U.S. patent application Ser. No. 17/807,994, filed onJun. 21, 2022, now U.S. Pat. No. 11,732,418, titled “COMPOSITESTRUCTURES FOR PACKAGING ARTICLES AND RELATED METHODS”, the contents ofwhich are expressly incorporated herein by this reference, and to whichpriority is claimed. U.S. patent application Ser. No. 17/807,994is acontinuation of U.S. patent application Ser. No. 16/828,382, filed onMar. 24, 2020, now U.S. Pat. No. 11,479,916, titled “COMPOSITESTRUCTURES FOR PACKAGING ARTICLES AND RELATED METHODS”, the contents ofwhich are expressly incorporated herein by this reference, and to whichpriority is claimed. U.S. patent application Ser. No. 16/828,382 is acontinuation of U.S. patent application Ser. No. 15/655,778, filed onJul. 20, 2017, now U.S. Pat. No. 10,633,799, titled “COMPOSITESTRUCTURES FOR PACKAGING ARTICLES AND RELATED METHODS”, the contents ofwhich are expressly incorporated herein by this reference, and to whichpriority is claimed. U.S. patent application Ser. No. 15/655,778 is acontinuation of U.S. patent application Ser. No. 14/213,394, filed Mar.14, 2014, titled, “COMPOSITE STRUCTURES FOR PACKAGING ARTICLES ANDRELATED METHODS”, the contents of which are expressly incorporatedherein by this reference, and to which priority is claimed. U.S. patentapplication Ser. No. 14/213,394 claims the benefit of U.S. ProvisionalPatent Application No. 61/782,291, filed Mar. 14, 2013, by inventorChristopher R. Tilton, the contents of which are expressly incorporatedherein by this reference, and to which priority is claimed.

FIELD OF THE INVENTION

The present embodiments relate generally to composite structures,particularly those used to fabricate storage articles and consumerpackaging, and related methods.

BACKGROUND

Packaging materials for product retail and shipping purposes aretypically sufficiently durable to allow reliable use of the materials.Typical considerations in the development of such materials includetheir barrier performance, tensile and tear strength, resistance towrinkling and scuffing, efficiency in manufacturing, as well asresistance to handling, infiltration by rodents and pests, and theability of the materials and packaging made therefrom to deter theft.The packages and packaging materials are also desirably relativelyinexpensive to manufacture, and are preferably attractive to thecustomer in appearance, print quality, feel, and touch to encourage useof the products as well as to enhance the product image or association.

SUMMARY

The present embodiments have several features, no single one of which issolely responsible for their desirable attributes. Without limiting thescope of the present embodiments as expressed by the claims that follow,their more prominent features now will be discussed briefly. Afterconsidering this discussion, and particularly after reading the sectionentitled “Detailed Description,” one will understand how the features ofthe present embodiments provide the advantages described herein.

Any or all of the below listed aspects may be a part of the presentembodiments:

Mineral particle densities within the polymer matrix of themineral-containing layer may be from about 2.4 g/cm³ to about 4.9 g/cm³.

Mineral particles within the polymer matrix of the mineral-containinglayer may comprise the cube and block class.

Calcium carbonate particles within the polymer matrix of themineral-containing layer may have about 18-80% particle diameters finerthan 6 Rm and about 33-96% particle diameters less than 10 μm.

A hardness of mineral particles within the polymer matrix of themineral-containing layer may be from about 2.0 to 4.0 Mohs.

Mineral particles within the polymer matrix of the mineral-containinglayer may have 0.05 to 0.5 maximum % on 325 mesh per ASTM D1199.

Mineral particles within the polymer matrix of the mineral-containinglayer may have a pH from about 8.5 to about 10.5.

The polymer bonding agent(s) within the mineral-containing layer mayhave densities from about 0.908 g/cm³ to about 1.60 g/cm³.

The polymer bonding agent(s) within the mineral-containing layer mayhave a physical melt flow index from about 4 g/m²/10 min to about 16g/m²/10 min.

Minerals may be fully dispersed within the polymer bonding agent matrix.

The polymer bonding agent(s) within the mineral-containing layer mayhave a molecular weight (Mz) from about 150,000 to about 300,000.

The polymer content weight of the mineral-containing layer may be fromabout 3.5 lbs/3 msf to about 50 lbs/3 msf.

The mineral-containing layer may have a modulus from about 1.8 GPa toabout 4.5 GPa.

About 40-60% of the mineral-containing layer may have a coefficient ofthermal expansion from about 1×10⁻⁶ in/in to about 8×10⁻⁶ in/in.

The mineral-containing layer may be applied to the fiber-containinglayer in coat weights from about 3 g/m² to about 20 g/m².

Surfaces of the mineral-containing layer may have a coefficient ofstatic friction from about 0.18 to about 0.59.

The mineral-containing layer may include a mixture of crystalline,semi-crystalline, and amorphous structures.

The polymer bonding agent(s) of the mineral-containing layer may havecrystallinity from about 60% to about 85%.

The mineral-containing layer may contain coupling agents from about0.05% to about 15% by weight.

The mineral-containing layer may contain from about 0.5% to about 10%plastomers and elastomers with densities from about 0.86 g/cm³ to about0.89 g/cm³ per ASTM D 792.

The mineral-containing layer may have differential scanning calorimetry(DSC) melting peaks from about 59° C. to about 110° C.

The mineral-containing layer molecular weight ranges (Mw) may be fromabout 10,000 to about 100,000.

About 10% to about 70% of the mineral-containing layer may have abranching index (g′) of about 0.99 or less as measured at the Z-averagemolecular weight (Mz) of the bonding agent.

The polymer bonding agent(s) of the mineral-containing layer may have anisotactic run length from about 1 to about 40.

The polymer bonding agent(s) of the mineral-containing layer may have aphysical shear rate from about 1 to about 10,000 at temperatures fromabout 180° C. to about 410° C.

The mineral-containing layer may have a basis weight from about 0.5lbs/msf to about 175 lbs/msf.

The polymer bonding agent(s) of the mineral-containing layer may havefrom about 20% to about 60%amorphous structure and from about 20% toabout 55% crystalline structure.

The polymer bonding agent(s) of the mineral-containing layer maycomprise polyethylene having an amorphous fraction from about 40% toabout 85%.

The mineral-containing layer may have a copolymer isotacticity indexfrom about 20% to about 50% as measured by the DSC method.

Mineral particles within the polymer matrix of the mineral-containinglayer may have an average surface area from about 1.0-1.3 m²/g to about1.8-2.3 m²/g.

Mineral particles within the polymer matrix of the mineral-containinglayer may have a Green Hunter reflectance range from about 91% to about97%, and a Blue Hunter reflectance range from about 89% to about 96%.

The fiber-containing layer may contain inorganic mineral coatings andfillers, including without limitation, kaolin clay, mica, silica, TiO₂,and other pigments.

The fiber-containing layer may contain vinyl and polymeric fillers.

A surface smoothness of the fiber-containing layer may be in the rangeof about 150 to about 200 Bekk seconds.

The fiber-containing layer may have an ash content from about 1% toabout 40%.

The fiber-containing layer may have any or all the characteristicspresented in the following table:

Fiber Aspect Ratio (Average) 5-100 Fiber Thickness (Softwood) 1.5-30 mmFiber Thickness (Hardwood) 0.5-30 mm Filled Fiber Content 1% to 30%Fiber Density 0.3-0.7 g/cm² Fiber Diameter 16-42 microns FiberCoarseness 16-42 mg/100 m Fiber Pulp Types Mechanical,Thermo-Mechanical, Chemi- (Single-to Triple-Layered) Thermo-Mechanical,and Chemical Permeability 0.1-110 m² × 10¹⁵ Hydrogen Ion Concentration4.5-10 Tear Strength (TAPPI ® 496, 402) 56-250 Tear Resistance (TAPPI ®414) m 49-250 Moisture Content 2%-18% by Weight

The fiber-containing layer may have any or all the characteristicspresented in the following table:

Fiber Tear Burst Weight Resistance Strength (lbs/3 msf) g/m² (Mn)Surface Roughness (kPa)  40-75  60-110  400-700 2.0-5.5 μm 140-300  75110-130  650-750 2.0-3.5 μm 175-400 115 180-190 1400-1900 100-2500mls/min 175-475 130 205-215 1600-2200 100-2500 mls/min 250-675 200315-330 1900-3200 100-2500 mls/min 500-950 300 460-195  500-4000100-2500 mls/min 700-1850

The mineral-containing layer may comprise a multilayer coextrusion, suchas up to six layers, with each layer having from about 0% to about 70%by weight mineral content with a polymer bonding agent.

A weight of the overall composite may be from about 2.5 lbs/3 msf toabout 150 lbs/3 msf.

The polymer bonding agent(s) of the mineral-containing layer maycomprise linear, branched, and/or highly branched polymers.

The polymer bonding agent(s) of the mineral-containing layer maycomprise polyolefin(s) having a number average molecular weightdistributions (Mn) from about 5,500 to about 13,000, a weight averagemolecular weight (Mz) from about 170,000 to about 490,000, and/or aZ-average molecular weight (Mz) from about 170,000 to about 450,000.

The mineral-containing layer may have a Mw/Mn ratio from about 6.50 toabout 9.50.

The mineral particles within the polymer matrix of themineral-containing layer may be surface treated at levels from about 1.6to about 3.5 mg surface agent/m² of the particle.

The mineral particles within the polymer matrix of themineral-containing layer may have a particle top cut from about d98 of4-15 microns and a surface area from about 3.3 m²/g to about 10 m²/g.

The mineral particles within the polymer matrix of themineral-containing layer may comprise CaCO₃ coated with fatty acidshaving from about 8 to about 24 carbon atoms, with a surface treatmentlevel from about 0.6% to about 1.5% by weight of the treatment, or fromabout 90% to about 99% by weight of the CaCO₃.

The mineral-containing layer may be from about 0.5 mil thick to about 5mil thick.

Examples of non-fiber content in the fiber-containing layer include, butare not limited to, about 50-95% of #1 clay or #1 fine clay, about 3-20%by part calcined clay, about 3-40% by part TiO₂, about 2-45% vinylacrylic, and from about 1% to about 35% protein binders, co-binders, ortri-binders.

The mineral-containing layer may contain incremental quartz-silicacontent.

A process for recycling the present composite structure may have rejectrates from about 10% to about 25% by weight of the starting composite,and screen plate efficiencies from about 60% to about 100%, with screenplates having the option of using hole, slotted, and contoured screenswith one screen behind the other with an A plate having the smallestperforations, an intermediary B plate, and a C plate having the largestperforations, using processes including high density, forward, andthrough flow cleaners having a diameter from about 70 mm to about 400 mmand particle process out of fibers having reject rates of about 0.1% toabout 30% and a particle removal efficiency from about 50% to 90% bymass, and particle sizes from about 150 microns to 0.05 microns.

A process for recycling the present composite structure may havefeed-accept pressures in the range of about 2 kPa to about 12 kPa onsmooth contoured and heavily contoured screens.

The present composite materials may have a pulper consistency from about3% to about 30%, pulping temperatures from about 100° F. to about 200°F., pulping times from about 10 min. to about 60 min., with pulping pHfrom about 6 to about 9.5±0.5, and screen holes from about 0.050″ toabout 0.075″ and slots from about 0.006″ to about 0.020″, drum pulpinghaving an RPM from about 9 to about 20, having 4 mm to about 8 mm holes,with hole-type screens with holes from about 0.8 mm to about 1.5 mm insize, coarse to fine screen holes and slots from about 0.150 mm to about2.8 mm, and screen rotor circumference speeds from about 10 mis to about30 m/s.

Certain of the present embodiments comprise a composite packagingstructure. The composite packaging structure comprises afiber-containing layer, and an outer layer bonded to thefiber-containing layer. The outer layer includes mineral particles in amatrix of a polymer bonding agent. The outer layer comprises from about20% to about 70% by weight of the mineral particles. The outer layer hasa density from about 1.05 g/cm³ to about 1.65 g/cm³, and a basis weightfrom about 4.5 lbs/3 msf to about 50 lbs/³ msf. The polymer bondingagent of the outer layer has a basis weight from about 1 lbs/3 msf toabout 20 lbs/3 msf. The mineral particles may be evenly dispersed in thepolymer matrix. The outer layer may be extruded. The outer layer mayhave a basis weight from about 7 lbs/3 msf to about 21 lbs/3 msf, andthe polymer bonding agent of the outer layer has a basis weight fromabout 2.45 lbs/3 msf to about 16.8 lbs/3 msf. The mineral particles ofthe outer layer may comprise calcium carbonate. The polymer bondingagent of the outer layer may comprise polypropylene. The outer layer maycomprise about 40% by weight of the calcium carbonate particles. Thepolymer bonding agent may have an isotactic run length from about 1 toabout 40. The polymer bonding agent may have a shear rate from about 1to about 10,000 at temperatures from about 180° C. to about 410° C. Theouter layer may provide hot tack operating ranges from about 25° C. toabout 225° C. having from about 1.0 N/mm to about 6.0 N/mm sealstrengths. The polymer bonding agent may comprise a polyethylenecopolymer, and the outer layer may provide hot tack operating rangesfrom about 80° C. to about 220° C. having from about 2.5 N/mm to about15 N/mm seal strengths. The outer layer may be about 20% to about 40%mineralized, with a structure that is about 20% to about 60% amorphousand about 20% to about 55% crystalline. The outer layer may have adensity from about 1.20 g/cm³ to about 1.35 g/cm³.

Certain of the present embodiments comprise a method of making acontainer from a sheet of a composite packaging structure. The sheetincludes a fiber-containing layer and a mineral-containing layer. Themethod comprises cutting the sheet into a desired shape, folding thesheet to form a three-dimensional shape, and heat-sealing abuttingsurfaces of the container to secure the abutting surfaces to oneanother. The heat sealing is performed under the following conditions: adwell time in the range from about 0.30 seconds to about 15 seconds, atemperature range from about 115° C. to about 240° C., and a sealpressure at or below about 0.80 MPa. The folding may be performedmanually or by machine. The three-dimensional shape may comprise a boxhaving a bottom wall, one or more side walls, and a lid portion. Thethree-dimensional shape may comprise a container liner. Thethree-dimensional shape may comprise an envelope. The peel strengthsbetween the heat-sealed abutting surfaces may range from about 1 J/m² toabout 45 J/m².

BRIEF DESCRIPTION OF THE DRAWINGS

The present embodiments now will be discussed in detail with an emphasison highlighting the advantageous features. These embodiments depict thenovel and non-obvious composite structures for packaging articles andrelated methods shown in the accompanying drawings, which are forillustrative purposes only. These drawings include the followingfigures, in which like numerals indicate like parts:

FIG. 1 is a graph illustrating the conductivity impact of filler loads;

FIG. 2 is a graph illustrating the impact of water on specific heatvalues;

FIG. 3 is a graph illustrating the impact of temperature on heatcapacity;

FIG. 4 is a graph illustrating polypropylene mineral composite specificheat capacities by filler load;

FIG. 5 is a schematic specific heat diagram for amorphous polymers;

FIG. 6 is a thermal conductivity diagram for amorphous polymers;

FIG. 7 is a graph illustrating thermal conductivity of mineral-filledpolypropylene by volume of fill;

FIG. 8 is a graph illustrating specific heat conductivity ofmineral-filled polypropylene;

FIG. 9 is a schematic side cross-sectional view of a multilayerpackaging composite material according to the present embodiments;

FIG. 9A is a detail view of the portion of FIG. 9 indicated by thecircle 9A;

FIG. 10 is a schematic side cross-sectional view of another multilayerpackaging composite material according to the present embodiments;

FIG. 11 is a schematic side cross-sectional view of a mineral-containingmaterial according to the present embodiments;

FIG. 12 is a schematic detail view of a pellet of a mineral-containingresin with mineral particles interspersed within a bonding agentaccording to the present embodiments;

FIG. 13 is a schematic side cross-sectional view of another multilayerpackaging composite material according to the present embodiments; and

FIG. 14 is a schematic side cross-sectional view of another multilayerpackaging composite material according to the present embodiments;

FIG. 15 is a container formed from a composite material according to thepresent embodiments;

FIG. 16 is a container liner formed from a composite material accordingto the present embodiments;

FIG. 17 is an envelope formed from a composite material according to thepresent embodiments; and

FIG. 18 is a display tray formed from a composite material according tothe present embodiments.

DETAILED DESCRIPTION OF THE ILLUSTRATIVE EMBODIMENTS

When forming packaging that contains food products and dry goods, heatsealability is often important for closures. Also, the packagingstructure preferably provides a barrier for moisture, oxygen, oils, andfatty acids. Other desirable characteristics include mechanicalperformance, aesthetics, cosmetics, resistance to chemicals,recyclability, heat sealability, surface energy, ink adhesion, inkwetability, film adhesion to fibers, improved surface for glue andadhesive application, and barrier performance (against oxygen, water,moisture, etc.). Therefore, extrusion coating fiber surfaces usingpolymers, (polyolefins being the most common) and biopolymers is commonpractice. Various diatomaceous earth mineral fillers and pigments aregenerally used including mica, silica, clay, kaolin, calcium carbonate(CaCO₃), dolomite, and titanium dioxide to name a few. The fillers offerimproved performance for barrier, opacity, increased stiffness, thermalconductivity, and strength. Fillers are normally less expensive thanpolymers and therefore a very economical component of the polymer layer.The most commonly used mineral fillers have densities in the range of2.4 to 4.9 g/cm³. Most polymers have densities in the range of 0.8 to1.4 g/cm³. Normally, the linear rule of mixtures can be used to predictthe density of a composite from those of the constituents and theirrelative amounts, where Pc, Py, and P are the densities of thecomposite, filler, and polymer, respectively, and My is the massfraction of the filler.

Pc=PfPp/PpMf+Pf(1−Mf)

Filler particles can vary in size and shape. Size can vary from 0.1micron to 10.0 micron mean particle size. An example of very finemineral particles include nano-precipitated calcium carbonate which areless than 100 nanometers in size. Ultrafine nano particles can rangefrom 0.06 microns to 0.15 microns. These ultrafine particles are usefulfor controlling rheological properties such as viscosity, sag, andslump. Mineral filler particles can have various shapes including e.g.,spheres, rods, cubes, blocks, flakes, platelets, and irregular shapes ofvarious proportions. The relationship between the particles' largest andsmallest dimensions is known as aspect ratio. Together, aspect ratio andshape significantly impact the particles' effect in a composite polymermatrix. In yet other examples, particle hardness relates to coarseness,color to layer cosmetics and opacity. Particle morphology suited for thepresent embodiments are primarily, but not limited to, the cube andblock shapes of salt and calcite having the characteristics shown inTable 1, below. Examples of cubic structures include calcite andfeldspar. Examples of block structures include calcite, feldspar,silica, barite, and nephelite.

TABLE 1 Mineral Physical Properties PARTICLE CLASS CUBE BLOCK TypeAspect/Shape Cubic, Prismatic, Tabular, Prismatic, Ratios: RhombohedraPinacoid, Irregular Length ~1  1.4-4 Width ~1 1 Thickness ~1   1-<1Sedimentation esd esd Surface Area 1.24 1.26-1.5 Equivalence

Mineral particles also often have higher specific gravity than polymers.Therefore, the density increases cost through elevated weight. Manyparticles are surface treated with fatty acids or other organicmaterials, such as stearic acid and other materials to improve polymerdispersion during compounding. Surface treatments also affect dry flowproperties, reduce surface absorption, and alter processingcharacteristics. The specific gravity range potential of the mineralsused in the present embodiments including pigments are from about 1.8 toabout 4.85 g/cm³.

It is advantageous to disperse fillers and pigments (which provideopacity and whiteness to the polymer composite) effectively in order toobtain good performance. For fillers, impact strength, gloss, and otherproperties are improved by good dispersion. For pigments, streakingindicates uneven dispersion, whereas a loss in tinting strength may beobserved if the pigment is not fully de-agglomerated. Agglomerates actas flaws that can initiate crack formation and thus lower impactstrength. In the present embodiments, agglomerates are preferably lessthan about 30 microns to preferably less than about 10 microns in size.

The thermal conductivity of the filler influences the processing of thepolymer composite as well as the conductivity of the final material. Inthe present embodiments, the thermal conductivity of themineral-containing composite layer applied to the fiber-containing layeris preferably in the range of about 0.02-3 WK⁻¹ m−1, ±20%, an order ofmagnitude higher than for polymers.

A filled layer can be up to four times more conductive than polymeralone. For unfilled polymers, data from the rule of mixtures does notexplain the outsized impact shown from actual data. Therefore, the levelof filler content (see FIG. 1 ) has an outsized impact on the transferof heat and processing during the composite's heating and coolingstages. Therefore, increased heat transfer rates readily impactmineral-containing extrudates and fiber adhesion during extrusioncoating and the finished composite layer's downstream heat-sealingcharacteristics.

Thermal conductivity and specific heat can be combined to determine theheating rate of a composite layer. Specific heat is reported as thecalories required to raise the temperature of 1 g of material by 1° C.Table 2, below, illustrates specific heat values for typical mineralfillers. Also, water content impacts specific heat as shown in FIG. 2 .

TABLE 2 Specific Heat Values for Common Minerals and Mineral Fillers 1Btu/lb ° F. = 4186.8 J/kg K. = kcal/kg ° C. and T (° C.)-5/9 [T(ºF)-32)] Specific Heat cP Specific Heat cP Specific Heat cP (Btu/lb_(m)° F.) (KJ/kg (Btu/lb_(m) ° F.) (KJ/kg (Btu/lb_(m) ° F.) (KJ/kg Product(kcal/kg ° C.) K) Product (kcal/kg ° C.) K) Product (kcal/kg ° C.) K)Calcite 32-100 F. 0.19 0.8 Cellulose 0.37 Graphite 0.17 0.71 Calcite32-212 F. 0.2 0.84 Chalk 0.22 0.9 Gypsum 0.26 1.09 Calcium 0.15 0.63Cobalt 0.11 0.46 Fluorite 0.22 0.92 Calcium carbonate 0.18 Clay 0.220.92 Fluorspar 0.21 0.88 Calcium Sulfate 0.27 Coke 0.2 0.85 Earth, dry0.3 1.26 Carbon, Diamond 0.12 0.52 Diamond 0.15 0.63 Garnet 0.18 0.75Carbon, Graphite 0.17 0.71 Dolomite Rock 0.22 0.92 Glass 0.2 0.84Carborundum 0.16 0.67 Granite 0.19 0.79 Glass, Crystal 0.12 0.5Limestone 0.217 0.908 Marble, Mica 0.21 0.88 Mercury 0.03 0.14 Emery0.96 Hermatite 0.16 0.67 Mica 0.12 0.5

The sum of the heat capacities of the constituent elements of a compoundprovides an approximation of the calories per gram formula weight. FIG.3 is an example of the relationship of temperature to heat capacity ofselected mineral fillers.

Composites have changing thermal conductivities due to composition.Table 3 shows the preferred neat polymers heat conductivity based upondensity within a range of about 0.11 to about 0.52 [W·M⁻¹·° K⁻¹].

TABLE 3 Example Neat Polymer Conductivity Polymer Density HeatConductivity 0.934 to 0.956 g/cm³ 0.33 to 0.052 0.908 to 0.925 g/cm³0.33 to 0.052

Diffusivity of a material is a good indicator of the ability to raiseits temperature and its ability to transfer heat throughout the heatseal process. Diffusivity=Thermal Conductivity/(Specific Heat×Density).The units in the SI system are m2/sec=W/(m·° K)+J/(kg·° K)×(kg/m³). Arelatively accurate average of each thermal property for the polymer andfillers can be determined by simple proportioning of the thermalproperties to the mix percentage. As an example, a polypropylene (“PP”)filled with 40% calcium carbonate has a diffusivity approximately 3.5times greater than that of neat PP. Thus, the filled PP takes much lessenergy to facilitate equal transfer, and transfers energy much faster,than the neat PP in relation to the mass of the output, resulting infaster and greater thermal transfer than neat PP. Higher heatdiffusivity and thermal transfer rate improve heat seal, peel strength,hot tack, and fiber tear.

Also, thermal transfer rates can accelerate and amplify the impact ofpre-adhesion conditioning methods found in extrusion lines, particularlyin advance of and during pre- and post-treatment, such as flame, corona,and plasma treatment. Thermal conductivity and temperature sensitivitysharply increase as mineral content increases, until it forms acontinuous network or percolation threshold. Once a continuous networkexists, added minerals have a rapidly diminishing impact. However,benefits remain, such as the reduction of polymer content, printability,adhesion, etc. The size and shape of the filler particles can helpdetermine the amount of filler needed to reach percolation levels, withsmaller, anisotropic fillers having a lower percolation threshold inmost cases.

Often, primers are need during extrusion coating production to improveadhesion of the extrudate to fibers. However, because of improvedadhesion characteristics during extrusion and later when the finishedcomposite is used for downstream heat seal packaging forming, less ofthe primer may be required or possibly a less expensive formulation maybe used having equal or better results. Advantageously, the primers maynot be needed at all. Examples of such primers include Michem® Flex PI883 water-based heat seal primer. Further, use of the primers at thepoint of printing as a heat seal accelerant, e.g., before, during, orafter rotogravure, offset, or flexo-printing, may be reduced or renderedunnecessary. Extrusion coating primers dry application weights can befrom about 0.5 to about 20.0 g/m². Example primer properties are, butare not limited to, density of about 0.55 to about 2.5 g/cc, a volatilescontent from about 60% to about 90%, pH from about 7.5 to about 9.9, andBrookfield viscosities of from about 40 cP to about 500 cP.

Also, the mineral-containing layer can improve heat seal performancewhen heat and pressure are used to bond structures known as “blisters”or “clamshells” to fiber-containing compartments. Equipment used to makethese types of packaging includes intermittent or continuous motionhorizontal and vertical form-fill-seal equipment or molded pulp formingequipment. Further, mineral-containing thermoplastics and polyolefinscan be used to coat single- and multilayer lids and sealing layersinline to form thermoplastic compartments.

Typically, heat seal coatings as well as polyolefin coatings are appliedto a fiber-containing or heat sealable layer such that the layer can besealed to the thermoplastic surface, forming the packaging article.However, unique properties of the mineral-containing layer can be usedto reduce or eliminate the need for polymer content in the finishedpackaging structures, or the coatings used to facilitate heat sealsbetween surfaces. Examples of these include, but are not limited to,Aquaseal® 2277 and Aquaseal® 2105, both by Paramelt Company. Thecoatings are often applied on the paper or other surfaces during theconverting process and before or after printing. The active ingredientsare typically delivered through aqueous and emulsion solutions andmixtures, using an organic vehicle, for example, an alcohol or aromatichydrocarbon such as xylene or a mixture thereof. Further, anotherexample includes a liquid epoxy resin emulsified in a solution of thecuring agent by stifling and the resultant solution dispersed with waterto the desired coating, having solid dispersions from about 2% to about60%. Another downstream product application might include single ormulti-layer layers including labels, liners, or other aspects when suchlabels require heat, but not limited to heat processes, duringmanufacturing or during application. The label surfaces might include arange mineral-containing layers, polymer and fiber-containing materialsand surfaces temporarily or permanently bonded to one or more inner orouter facing surfaces of the label structure before or after applicationto the product or products being applied.

Resin and composite extrudate sensitivity to heat becomes importantduring extrusion coating and extrusion lamination production. Smallalterations during processing have an outsized impact upon pre- andpost-extrusion results. Table 4 is a sample, but not limited to,extrusion coating production ranges for identified mineral-filledresins. In Table 4, the melt index measurements were stated under theguidelines of ASTM method D1238-04, and the density measured under theguidelines of ASTM standard method D1501-03.

TABLE 4 Operating Parameters, Mineralized Composite Resins, Monolayer,Coextrusion, and Multilayer Mineral-Containing Composites, toFiber-Containing Layers ROLL

Extruder #2-#6 Maximμm ranges (coextrusion) or Plus & Minus as aExtruder #1 separate % of stated value Comments below do not Monolayerdownstream units or stated value represent limitations RESIN EarthCoating Earth Coating SUPPLIER Standridge Standridge Color Color GRANDNUMBER TBD TBD MELT FLOW-Carrier EST: 16 g/10 EST: 16 g/10 min. 4g10/min to 16 Interspersed and non- resin(s)/bonding agent min. g/10 min.interspersed COMPOUND DENSITY 1.25 g/cm3 1.25 g/cm3  1.01-4.90 Molecularweight from g/cm3 (Mz 150,00 to 300,00) MINERAL CONTENT 40% 40% Generalmineral Interspersed and non- content 15-60% interspersed by weight MELTTEMPERATURE 590º F (307º C.) TBD ±20% DESIRED BARREL   1600-2200 psi TBD  1200-2500 psi From 1 to 6 extruders PRESS. Composite Melt Flow    2-12 g/    2-12 2 g/10 min-14 Interspersed and non- 10 min g/10 ming/10 min interspersed Air Gap 8″    4″-12″    4″-16″ Die Gap0.025″-0.030″ 0.025″-0.040″ 0.020″-0.050″ From 1 to 6 CoextrusionMonolayer and Coextrusion or separate downstream #2-#6 Co-layersTEMPERATURE SETTINGS Initial Settings Maximμm Settings Die Zone MaximμmAdjust Die Barrel Zones Adjustment Barrel Zone Melt Temperature 590º F.Up to ±25% BARREL ZONE #1 405º F. Up to ±35% Die Zone 1 585º F. ±25%BARREL ZONE #2 540º F. Up to ±35% Die Zones 2-10 585º F. ±25% (asapplicable to equipment) BARREL ZONE #3 575º F. Up to ±35% Die Zone 11(as 585º F. ±35% applicable to equipment) BARREL ZONE #4 590º F. Up to±35% BARREL ZONE #5 590º F. Up to ±35% Other Barrel Zones, if 590º F. Upto ±35% Other die zones if Up to ±35% applicable on specific applicableequipment

The heat capacity of the polymer composite represents the amount ofenergy required to heat up and cool down the material whereas theconductivity determines the speed of the heat transfer. It is possibleto calculate the specific heat capacity for a composite using the linearrule of mixtures if the capacities of the two phases and their volumefractions are known. FIG. 4 shows selected specific heat values formineral-filled polypropylene. Normally, units of J-L⁻¹K⁻¹ are used toexpress specific heat capacity. For composites, however, this is notappropriate because one needs to know the heat capacity of a part whosevolume is determined by the volume (not mass) of the polymer bondedthrough extrusion to the fiber surface. The volume specific heatcapacities of mineral fillers in densities from about 1.95 to about 4.90g/cm³ with particle distributions from about 0.75 micron to about 10micron mean particle size (1900-2600 J-L⁻¹ ⁻¹) are similar to those ofpolymers (1500-3000 J-L⁻¹ K⁻¹), so fillers aid cooling in terms of speedof heat removal, but not through a reduction in heat capacity. Mineralparticle size distribution also plays a role in thermal conductivity.

These attributes are key in adhesion of the polymer content to fiber andclay-coated fiber surfaces during extrusion production when theextrudate makes contact with the fiber surface. The filler has thecapacity to absorb heat energy at approximately the same levels duringshear and heating. However, its efficiency in discharging the heatproves invaluable for adhesion to fiber and clay-coated fiber surfacesas well as adhesion to flexible film surfaces. The estimated within ±10%preferred specific, but not limited to, heat ranges expressed in cal/g·°C. for selected minerals are: Calcium Carbonate 0.205, Kaolin 0.22, Talc0.208, Mica 0.206, Feldspar 0.21, Wollastonite 0.24, Barite 0.11, andSilica 0.19.

A schematic specific-heat diagram for amorphous polymers is shown inFIG. 5 . The inflection point corresponds to the glass-transitiontemperature, T. Typically, the variation in the specific-heat ofamorphous materials can be about 50-70% between the processingtemperature and room temperature.

Unlike amorphous polyolefins, a crystalline and semi-crystallinestructure hysteresis is observed between the melting and thecrystallization peaks, due to supercooling. Additionally, thecrystallization process depends on the cooling rate, as thecrystallization peak shifts to lower temperatures at higher coolingrates. These characteristics become critical aspects of mineralizationaffecting adhesion and the various amorphous-crystalline polymer mixesunder mineral loads from about 20% to about 70% by weight of polymermineral resin. This is particularly important in that functionallyfilled amorphous polymers and mixes of amorphous, crystalline, andsemi-crystalline polymers have a comparable heat capacity. However, asmineralization filling occurs in the polymer matrix, the crystallizationpeak becomes highly efficient as heat is discharged earlier and morequickly. Using this effect, interspersed (polymers layered throughcoextrusion) or non-interspersed (mono-layer) extrusion combinations canresult in advantageous heat seal characteristics and at the same timeuse less polymer mass. Also, using functional minerals, hot tackperformance can be improved by optimizing the mix of amorphous to highlycrystalline polymers. Commonly available specific heat data are measuredunder a heating scan. The polymer, however, undergoes high cooling rate(quenching) during the extrusion process. While this will not affect thetransitions of amorphous polymers significantly, the transition shiftsfor semi-crystalline materials can be dramatic. Upon mineralization,significant shifts could be seen in amorphous polymers.

Thermal conductivity is one of the most important properties foradhesion and heat seal performance. Similar to specific heat, thermalconductivity also exhibits variations from room temperature toprocessing temperature. Thermal conductivity, K, is reported ascal/cm·s·° C. Inorganic contents have values less than 1 to 8×10⁻³(±20%). Their constituent atoms are free to rotate and dissipate theeffects of thermal energy, whereas fillers are rigidly fixed groups ofatoms. Most polymers have a K of less than one order of magnitude thanminerals. When these values are multiplied by density to obtain cal/cm3,the range for plastics and preferred fillers for the present embodiments±20% are 0.35 (plastics) to 0.56 cal/cm³.

Because mineralized polymer composites maintain sufficient levels ofheat capacity, elevated thermal conductivity contributes to improvedheat sealing and hot tack performance on monolayer and multilayerpolyolefin-mineral composites to fiber surfaces, resulting insubstantially improved peel strengths. Shown in FIG. 6 is a schematicthermal conductivity diagram for amorphous polymers. Thermalconductivity can increase approximately 1% to approximately 300%depending upon polymer type and mineral filler loads and filler type.Thermal conductivity consists of two regions in a piece-wise linearmanner. Thermal conductivity remains constant when temperature is aboveTg and decreases linearly when temperature is below T. The slope of theline below Tg is about 0.04 W/m·K per 100° C. and is reasonablyuniversal to all pure, amorphous polymers. Thermal conductivity offunctionally filled polymers, however, shows an abrupt increase whentemperature drops below the crystallization temperature, Tc. This isbecause of the appearance of the crystalline phase, which createsregions of increasing high thermal conductivity, as shown by the arrowin FIG. 6 .

Functionally mineralized amorphous polymers can show an increase whentemperature drops below the crystallization temperature. Thischaracteristic impacts heat sealing and hot tack extrusion adhesionperformance in amorphous and crystalline polymer mixes. In FIG. 6 , theupper line represents estimated values for mineral containing resins.FIG. 7 shows the general relationship of selected filler at differentvolumes when added to polypropylene (PP). Further, FIG. 8 shows specificheat conductivity values of mineralized PP.

FIG. 8 illustrates temperature dependence of the specific heat capacityof polypropylene filled with 45-vol % magnetite and barite. The symbolsare measured values, the lines represent linear fits. Additionally, thepreviously stated characteristics provide the mineral-containing polymercomposite to effect high performance heat sealing to other polymer andfiber surfaces using less by weight polymer mass to achieve functionalheat seal tack and adhesion. Table 5, below, illustrates preferredpolymer weight ranges, but not limited to, mineral composite extrudateproviding combinations of one or more of fiber adhesion, fiber tear,heat seal, and heat seal tack.

TABLE 5 Polymer and Filler Mass for Composite Adhesion to Fibers andHeat Seal Tack Density Total Mass Poly Content Extrudate (g/cm³) (lbs/3msf) (lbs/3 msf) Neat Polymer 0.88-0.98 3.5-50 3.5-50 20% to 65% Filled1.05-1.65 4.5-50 1.0-20.0

Interspersed (coextruded) and non-interspersed (monolayer) polymerlayers effecting thermal transfer and thermal capacity when applied tofiber and clay-coated surfaces via extrusion coating therefore canresult in far superior heat seal and adhesion performance, therebylowering costs by reducing the total polymer content in the structure.Because polymers are considered a contaminant to paper recycling, otherbenefits include an improved environmental footprint through reducedpolymer contamination content in the overall mixed material packagingstructure, e.g., polymer and fiber construction, improving the potentialfor recyclability. The environmental impact of finished, converted, andprinted packaging is an important aspect of manufacture. Generally, whenpolymers are used to coat fibers, the polymer content is considered acontaminant to the recycling process of the fiber substrate, renderingthe packaging unrecyclable and unrecoverable. However, if the polymercontent is sufficiently reduced as a percentage of the packagingstructure, the packaging material may then be deemed recyclable bypublished standards known within the recycling industry. For example,one publication establishing such recycling standards is the ScrapSpecification Circular, published annually by the trade group “Instituteof Scrap Recycling.” A commonly sought-after qualification forpaperboard recycling is the Residential Mixed Category, found on page 32of the Circular. In order to achieve this standard, the percentage ofpolymer contamination should be below a certain level. Mineral fillersare not considered a contaminant. Therefore, increasing mineral contentby weight provides improved recycling characteristics of theextrusion-coated paperboard.

However, as the amount of mineral content diminishes, machinability andresin stability during processing is affected. The present embodimentsoffer unique polymer composite structures and blends optimizing themineral content and improving processing, greatly improving therecyclability of the finished packaging materials. Table 6, below,illustrates estimated fiberboard weight ranges, but not limited to,required to qualify for recyclability standards once the extrudate bondsto the fiber-containing surface during extrusion coating or extrusionlamination.

TABLE 6 Estimated Fiber Mass Required to Achieve ISRI RecyclingQualifications, Residential Mixed Category, When Polymer CompositeLayer(s) are Combined with Natural Fibers Extrudate Mass Polymer ContentFiber Weight Required Extrudate (lbs/3 msf) (lbs/3 msf) (lbs/3 msf) NeatPolyolefin 7-21   7-21 >350 20% to 65% Filled 7-21 2.45-16.8 >120

Heat deflection temperature “HDT” can play a role in post-extrusion heatsealing of the polymer composite to fiber and clay-coated fibersurfaces. Further, HDT can affect adhesion and bonding of the extrudateonto the fiber surface during extrusion processing, which is a criticalaspect of post extrusion performance. The HDT provides insights to themaximum temperature a material can withstand before it starts to deformunder load. HDT increases with mineral fillers and the trends aresimilar for modulus.

The Adding filler content increases HDT. The maximum HDT is for highloadings of high aspect ratio filler, as occurs at the temperature inwhich the polymer phase softens. This is very important as the polymercomposite is softened upon contact with fibers during and right afterextrusion and during the heat seal cycle at or near the heat sealactivation temperature during specific dwell and compression settings.Novel resin blend combinations found in interspersed andnon-interspersed polymer layers applied on fiber and clay-coatedsurfaces can result in far superior heat seal and fiber adhesionperformance. For semi-crystalline polymers the maximum HDT is also forhigh loadings of anisotropic filler, but the limiting HDT is near themelting point of the polymers. For example, the HDT of PP homopolymerwith a 20% filler load is 72° C. and up to approximately 82° C. fromabout 40% to about 50% by weight loading. This data is similar forpolyolefins.

Most minerals have higher moduli than the polymer into which they arebonded. The mineral raises the modulus, and the amount of stiffeningdepends on the volume percent of the filler and the shape of theparticles. Usually, modulus is plotted versus the weight percent of thefiller.

The isotropic fillers such as calcium carbonate and dolomite give theleast stiffening per unit volume added. Glass fibers, having the highestaspect ratio, offer the greatest stiffening. Particle size has no directeffect on the modulus of thermoplastics. The orientation of anisotropicfillers can change modulus, and high shear that occurs during extrusionorients the filler particles. Extruded composite polymer coatings havingincreased modulus can positively impact the mechanical attributes of thecoating, providing increased heat seal performance at lower coat weightsthan non-filled polymer coatings. For example, the modulus of a PPhomopolymers is 1.4 GPa. At 5% by weight of mineral filler load of CaCO3particles, the modulus increases to 1.8 GPa, at 10% filler load themodulus increases to 2.1 GPa, at 20% filler load the modulus increasesto 2.5 GPa, and at 40% filler load the modulus increases to 3.1 GPa.Modulus could increase up to 4.5 GPa with mineral loads on or about 60%.Thermal expansion characteristics also play a role in polymer compositeperformance.

The coefficient of thermal expansion (CTE) represents the amount that amaterial expands or contracts with changes in temperature. A positivevalue indicates that the material expands when heated. The CTE may varywith temperature, but for the sake of this example, we will considerapproximate values. The CTE for thermoplastics is usually in the rangeof ˜10×10⁻⁵ mm²/° C.±20%. This is approximately an order of magnitudemore than for mineral fillers ˜10×10⁻⁶ mm²/° C. Also, the CTE can bereported as units per unit of linear dimensions per ° C. for a specifiedrange of temperature. The CTE of cubical expansion is reported as thevolume increase per unit volume of material per ° C. Most fillers expanddifferently in different directions owing to non-uniform composition orcrystalline structure. CTE values for preferred inorganic fillers lie inthe range of about 1 to 8×10⁻⁶ in/in. The CTE has practical impact inthat it predicts how much an extruded polymer coating will shrink uponcooling. Less shrinkage can result in improved adhesion to fibersurfaces and improved heat seal characteristics to an opposing polymersurface or heat sealing to form.

When using extrusion coating methods to bond the mineral containinglayer to fibers, mineralized pellets are generally in the range, but notlimited to, ⅛″ long and ⅛″ in diameter or less. The preferred extrusioncoating adds significant costs and therefore the materials used arepreferably inexpensive and provide the high performance. Increasingprocessing speeds and efficiencies is desirable. During the extrusionprocess, several steps are used to improve the printability, inkwet-ability, and adhesive bonding potential of the polymer surface.Primers are commonly used to improve the extrudate adhesion to fibers.The primers can be applied as a dispersion or as a solution. Yet anotherprimer includes polyethyleneimine or “PEL” Mineral-containing polymercomposites work well with primers including shellac, organic titanite,urethane, polyethylene imine, ethylene acrylic acid, and polyvinylidenechloride. Other primers include but are not limited to the reactionproduct of an epoxy resin and acidified amino-ethylated vinyl polymeremployed with glycidyl ethers of polyhydroxy compounds.

Mineral loaded polymer composites normally improve primer performancewhen applied from between 3 gsm (grams per square meter) to 20 gsm coatweights. Mineral loaded polymer composites can also heat seal to primedfiber surfaces during packaging production. This technique oftenmitigates the need for a polymer-to-polymer heat seal requirement, thusimproving economics and the environmental footprint. Also, pre-heatingof the fibers is common to improve the polymer adhesion to the fibersubstrate as well as exposure to ozone. In addition to pre- andpost-treating, polymer composite adhesion, bonding, fiber tear, and peelstrength achieved after the extrudate makes contact with the fibers is acritical aspect of the extrusion coating process.

Another common practice is post-treating using corona or plasmatreatment. The polymer layer increases in surface energy to improve inkwet-ability and ink adhesion as well as more favorable reaction whengluing, laminating, or adhering the polymer surface to another surfaceof the package. Yet another important polymer characteristic is theamount of dry friction on the surface of the polymer. Dry frictionresists relative lateral motion of two solid surfaces in contact. Dryfriction is subdivided into static friction, (stiction), betweennon-moving surfaces, and “kinetic” friction between two moving surfaces.The coefficient of friction (COF) is a dimensionless scalar value thatdescribes the ratio of the force of friction between two bodies and theforce pressing them together. COF ranges from near zero to greater thanone. High COF is generally very useful for improved ink wetability andfor gluing and adhesive results. Polymer surfaces such as polyethylene(PE) normally have a COF from 0.15 to 0.35. However, COF for mineralizedpolymer surfaces can be in the estimated range from about 0.18 to about0.59. The higher number representing increased friction.

Some of the many benefits of neat, unfilled, polyolefin plastomers arefavorable heat seal and optics characteristics in general. However,expensive additives with undesirable side effects are often required toprovide machinability in filling operations. In filling, the lower theCOF, the more easily handled the polymer surface during gluing,printing, and converting. As the polyolefin density decreases, opticsand sealability improve, however, the film surface becomes tacky and theCOF increases. However, functional mineral loadings can increase densityand improve heat sealability without increasing the COF. Polyolefins areone group of resins used to form the film structure. Polyolefins arethermoplastic resins polymerized from petroleum-based gases. The twoprincipal gases are ethylene and propylene. Ethylene is the raw materialfor making polyethylene (PE) and ethylene copolymer resins and propyleneis the main ingredient for making polypropylene (PP) and propylenecopolymer resins. Polyolefin resins are classified as thermoplastics,which means that they can be melted, solidified, and melted again.Mineralized polyolefin resins for extrusion coating are sold intranslucent pellets and white pellets. Mineralized polymer resinssometimes contain additives, such as thermal stabilizers, or arecompounded with colorants, antistatic agents, UV stabilizers, etc. Thefilm structure of the present embodiments uses significant mineralfiller content(s) interspersed within the film structure and foundwithin one or more composite layers.

Polyolefin resins are a mixture of crystalline and amorphous structures.Amorphous polymers tend to shrink less on cooling than semi-crystallinepolymers such as PE or PP. Due to the macromolecular structure ofpolymers, shrinkage can occur 24 to 48 hours after cooling. Because theCTE of fillers is far lower than for polymers, the addition of mineralfillers results in less shrinkage than the parent polymer combination.When the filler is combined with novel combinations of amorphous andsemi-crystalline polymers, advantageous adhesion and heat sealcharacteristics emerge.

Molecular chains in crystalline areas are arranged somewhat parallel toeach other. In amorphous areas they are random. This mixture ofcrystalline and amorphous regions is essential to the extrusion of goodextrusion coatings. The crystals can act as a filler in the matrix, andso can mineralization, improving some mechanical properties. A totallyamorphous polyolefin would be grease-like and have poor physicalproperties. A totally crystalline polymer would be very hard andbrittle. HDPE resins have molecular chains with comparatively few sidechain branches. Therefore, the chains are packed closely together.Polyethylene, polypropylene, and polyesters are semi-crystalline. Theresult is crystallinity up to 95%. LDPE resins have, generally, acrystallinity ranging from 60% to 75%, and LLDPE resins havecrystallinity from 60% to 85%. Density ranges for extrusion coatingresins include LDPE resins that range from 0.915 to 0.925 grams percubic centimeter (g/cm3), LLDPE resins have densities ranging from 0.910to 0.940 g/cm3, and MDPE resins have densities ranging from 0.926 to0.940 g/cm³. HDPE resins range from 0.941 to 0.955 g/cm³. The density ofPP resins range from 0.890 to 0.915 g/cm³.

Addition of a mineral filler to the polymer results in a rise inviscosity. The addition of filler may also change the amount ofcrystallinity in the polymer. As polymer crystals are impermeable to lowmolecular weight species, an increase in crystallinity also results inimproved barrier properties, through increased tortuosity. This effectis expected to be prevalent for fillers that induce a high degree oftrans-crystallinity. Some minerals can change the crystallizationbehavior of some thermoplastics and thus the properties of the polymerphase are not those of virgin material, providing novel characteristicsduring processing and in the performance of the finished compositestructure. Thermoplastics crystallize in the cooling phase and solidify.Solidification for semi-crystalline polymers is largely due to theformation of crystals, creating stiffer regions surrounding theamorphous area of the polymer matrix. When used correctly, mineralfillers can act as nucleating agents, normally at higher temperatures.This process can provide mechanical properties in the polymer compositefavorable to high barrier performance and adhesion to fiber surfaceswithout a detrimental effect on heat sealing characteristics. Mineralscan begin to significantly effect crystallinity when used from about 15%to about 70% by weight of the polymer composite. Some of the factorsinfluencing mechanical adhesion to paper include extrudate temperature,oxidation, and penetration into the fibers. Mineral onset temperaturesof the polymer extrudate influence cooling rate upon die exit to the niproller, which can be adjusted by the extruder air gap setting. Other keyfactors include the mass of the polymers of the polymer interface layer.The crystalline onset temperatures may vary. Examples are shown in Table7 below.

TABLE 7 Selected Polymers with Estimated Mineral Onset TemperaturesUnfilled Polypropylene 120-122º C. Calcium Carbonate 120-125º C.Dolomite 120-131º C. Talc 120-134º C. Silica 120-122º C. Mineral Fiber120-122º C. Mica 120-124º C.

Further, homogeneous blends of solid olefin polymers with varyingdensities and melt indexes can be mixed within the mineral compositelayer, either interspersed or non-interspersed through coextrusion. Themineral-containing composite layer can be applied and bondedsubstantially and continuously on at least a fiber-containing layerusing extrusion or extrusion lamination, including blown film, cast, orextrusion coating methods. Polymer content of the mineral-containinglayer can be used as a tie layer for interspersed and non-interspersedconstructions as well as particle bonding agents within each individuallayer. These bonding agents or tie layers can include individually, orin mixtures, polymers of mono-olefins and diolefins, e.g. polypropylene,polyisobutylene, polybutylene, poly-4-methyl-pentylene, polyvinylcyclohexane, polyisoprene or polybutadiene, homogeneous metallocenecopolymers, and polymers of cycloolefins, e.g. cyclopentene ornorbornene, polyethylene, cross-linked polyethylene, ethylene oxide andhigh density polyethylene, medium molecular weight high densitypolyethylene, ultra heavy weight high density polyethylene, low densitypolyethylene, very low density polyethylene, ultra-low densitypolyethylene; copolymers of mono-olefins and diolefins with one anotheror with other vinyl monomers, e.g. ethylene/propylene copolymers, linearlow density polyethylene, and blends thereof with low densitypolyethylene, propylene but-1-ene, copolymers ethylene,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/octene copolymers, ethylene/methylpentene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers, COC,ethylene/I-olefin copolymers, the I-olefin being produced in situ;propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/vinyl cyclohexene copolymers, ethylene vinyl acetatecopolymers, ethylene/alkyl methacrylate copolymers, ethylene/acrylicacid copolymers or ethylene/acrylic acid copolymers and salts thereof(ionomers) and tera-polymers of ethylene with propylene and diene, suchas, for example, hexadiene, dicyclopentadiene or ethyl-idenenorbornene;homopolymers and copolymers that may have any desired three dimensionalstructure (stereo-structure), such as, for example, syndiotactic,isotactic, hemi isotactic or atactic stereo block polymers are alsopossible; polystyrene, poly methyl styrene, poly alpha-methyl styrene,aromatic homopolymers and copolymers derived from vinyl aromaticmonomers, including styrene, alpha-methyl styrene, all isomers of vinyltoluene, in particular p-vinyl toluene, all isomers of ethyl styrene,propyl styrene, vinyl biphenyl, vinyl naphthalene and blends thereof,homopolymers and copolymers of may have any desired three dimensionalstructure, including syndiotactic, isotactic, hemi isotactic or atactic,stereo block polymers; copolymer, including the above mentioned vinylaromatic monomers and commoners selected from ethylene, propylene,dienes, nitriles, acids, maleic anhydrides, vinyl acetates and vinylchlorides or acryloyl derivatives and mixtures thereof, for examplestyrene/butadiene, styrene/acrylonitrile, styrene/ethylene(interpolymers) styrene/alkyl-methacrylate, styrene/butadiene/alkylacrylate, styrene/butadiene/alkyl methacrylate, styrene/maleicanhydride, styrene copolymers; hydrogen saturated aromatic polymersderived from by saturation of said polymers, including poly-cyclohexylethylene; polymers derived from alpha, beta-unsaturated acids andderivatives; unsaturated monomers such as acrylonitrile/butadienecopolymers acrylate copolymers, halide copolymers and amines from acylderivatives or acetals; copolymers with olefins, homopolymers andcopolymers of cyclic ethers; polyamides and copolyimides derived fromdiamines and dicarboxylic acids and or from amino carboxylic acids andcorresponding lactams; polyesters and polyesters derived fromdicarboxylic acids and dials and from hydroxycarboxylic acids or thecorresponding lactones; blocked co-poly-ether esters derived fromhydroxyl terminated polyether; poly-ketones, poly-sulfones, poly-ethersulfones, and poly-ether ketones; cross-linked polymers derived fromaldehydes on the one hand phenols, ureas, and melamines such asphenol/formaldehyde resins and cross-linked acrylic resins derived fromsubstantial acrylates, e.g. epoxy acrylates, urethane acrylates orpolyester acrylates and starch; polymers and copolymers of suchmaterials as poly lactic acids and its copolymers, cellulose,polyhydroxy alkenoates, polycaprolactone, polybutylene succinate,polymers and copolymers of N-vinylpyrrolidone such aspolyvinylpyrrolidone, and crosslinked polyvinylpyrrolidone, ethyl vinylalcohol. More examples of thermoplastic polymers suitable for themineral-containing composite include polypropylene, high densitypolyethylene combined with MS0825 Nano-reinforced POSS polypropylene,thermoplastic elastomers, thermoplastic vulcanites, polyvinylchloride,polylactic acid, virgin and recycled polyesters, cellulosics,polyamides, polycarbonate, polybutylene terephthalate, polyesterelastomers, thermoplastic polyurethane, cyclic olefin copolymer;biodegradable polymers such as Cereplast-Polylactic acid, Purac-LactidePLA, Nee Corp PLA, Mitsubishi Chemical Corp GS PLS resins, NatureworksLLC PLA, Cereplast-Biopropropylene, Spartech PLA Rejuven 8, resins madefrom starch, cellulose, polyhydroxy alkenoates, polycaprolactone,polybutylene succinate or combinations thereof, such as Ecoflex FBX 7011and Ecovio L Resins from BASF, polyvinylchloride and recycled andreclaimed polyester such as Nodax biodegradable polyester by P & G.

The mineral-containing layer can include coupling agents from about0.05% to about 15% of the weight of the mineral-containing layer. Theagents aid in the mixing and the filling of the mineral into the polymermatrix. Functional coupling groups include (Pyro-) phosphate, Benzenesulfonyl and ethylene diamino. These can be added to thermoplasticsincluding polyethylene, polypropylene, polyester, and ethyl vinylalcohol, aluminate, siloxane, silane, amino, malice anhydride, vinyl andmethacrylic. The results of these combinations improve adhesion tofibers, heat seal strength, heat seal activation temperatures, surfaceenergy, opacity, and cosmetics. Mineral content can include, but is notlimited to, wollastonite, hydrated and non-hydrated, magnesium silicate,barium sulfate, barium ferrite, magnesium hydroxide, magnesiumcarbonate, aluminum trihydroxide, magnesium carbonate, aluminumtrihydroxide, natural silica or sand, cristobalite, diatomite,novaculite, quartz tripoli clay calcined, muscovite, nepheline-syenite,feldspar, calcium sulfate-gypsum, terra alba, selenite, cristobalite,domite, silicon mica, hydrated aluminum silicates, coke, montmorillonite(MMT), attapulgite (AT) carbon black, pecan nut flour, celluloseparticles, wood flour, fly ash, starch, TiO2 and other pigments, bariumcarbonate, terra alba, selenite, nepheline-syenite, muscovite,pectolite, chrysotile, borates, sulfates, nano-particles of the abovefrom 0.01 to 0.25 micron particle size, and precipitated and groundcalcium carbonate. Among, but not limited, procedures generallyinvolving the use of polymerization initiators of catalysts for thepolymerization of butene-I monomer to polymers of high molecular weight,preferably catalytic systems used in such procedures are the reactionproducts of metal alkyl compounds such as aluminum triethyl, and a heavymetal compound, such as the trihalides of Groups IV-VI metals of theperiodic table, e.g., titanium, vanadium, chromium, zirconium,molybdenum and tungsten. The formation of polymers exhibitingsubstantial isotactic properties as wells as the variations in themolecular weight and the nature of the polymerization catalyst,co-reactants, and reaction conditions. Suitable, but not limited to,isotactic polybutylenes are relatively rigid at normal temperatures butflow readily when heated, and they most preferably, should show goodflow when heated, expressed in melt flow. Applicable isotacticpolybutylenes should show a melt flow of from 0.1 to 500, preferably 0.2to 300, more preferably from 0.4 to 40, most preferably 1 to 4. Otherpolymers expressed within the contents of the present specificationshould also be considered within these parameters.

Regarding the mineral-containing composite layer, upon substantially andcontinuously bonding to the fiber-containing using extrusion coating orextrusion lamination techniques, the layer of which can then be used toform a laminated structure of which the mineral-containing layer can beused as a peel coat onto a desired backing material. The best peel seal,for example, to the mineral-containing layer of the composite, may beselected from poly-4-methyl pentene, nylon, high-density polyethylene(HDPE), aluminum foil, polycarbonate polystyrene, polyurethane,polyvinyl chloride, polyester, polyacrylonitrile, polypropylene (PP),and paper. An example extrusion process can be accomplished with a screwor pneumatic tube. Sometimes the mineralized polymers can be combinedwith such materials as plasticizers lubricants, stabilizers, andcolorants by means of Banbury mixers. The resulting mix is then extrudedthrough rod shaped dies and chipped into pellets. Pelletized mineralizedpolymer can then enhance the mineral and other content by “letting down”the resin pellet mix with inline or offline mixing capability beforebeing fed into the end of a, for example, screw-type extruder, heated,and mixed into a viscous fluid or semi-fluid in the extruder barrel forfurther processing to the die. Further, when properly dispersed theinteraction between the mineral particles and the polymer contentwithout covalent bonding, results in improved van der Waals forces thatprovide attraction between the materials. This interaction results insome adhesion in the composite during extrusion, resulting in anabsorbed polymer layer on the filler surface.

The absorbed layer has restricted movement, and therefore has differentproperties than those surrounding the free polymer. The modifiedparticle layer is called the “interphase.” When using finer groundfillers with lower mean particle sizes, the effect of the inter-phasebecomes significant enough to increase barrier performance because ofthe depth and frequency of the modified particles along the surface ofthe extruded polymer composite. The restricted polymer layer has lessfree volume than the bulk and this reduces permeability. The improvedtortuosity can provide significant barrier performance improvements, asillustrated in various tables contained within this specification.

Heat sealing from fiber to polymer layer, from polymer layer to polymerlayer, and heated polymer layers making contact with fiber layers duringextrusion coating, are the most commonly used techniques forconstructing packaging materials that are then heat-sealed duringpackage forming. Packages are formed after extrusion coating usingdifferent heat-sealing technologies, such as ultrasonic welding, hot airwelding, chemical adhesives, bar heat sealing, and impulse heat sealing.The molecular process that occurs during the heat sealing undercompression or extrusion coating of a polymer layer to fibers, havingsemi-crystalline polymer content, is the interface between the polymercurtain or layer and fiber surface. Here, van der Waals forces arise inthe contact area of the materials. These considerations combined withthe unique attributes of the mineral content dispersed within thepolymeric matrix of both monolayer and multilayer mineral compositelayers impact the application of heat that initiates the melting ofsemi-crystalline polymers, causing the polymer molecules to betterdiffuse across the interface. Given sufficient time, the diffusedpolymer molecules and mineral content will become entangled with eachother. The heat capacity of the mineral-containing layer is generallyabout the same as a neat polyolefin layer, accelerating fiber bonding atsufficient temperatures, particularly at very short dwell intervals withhigh heat levels, for example, using hot air sealing from about 0.23second dwell and above and heat ranges from about 925° F. to about1,100° F. Heat seal pressure requirements are generally less, but in thesame range as, neat polyolefins from about 20 psi to about 80 psi.

Depending upon mass of mineralized polymer layer and percentage ofmineral content by weight and other factors, heat seal activationtemperatures range from about 350° F. to about 1100° F. With or withoutprimers, during extrusion coating of either monolayer or multilayermineral composite layers to fiber, 75% to 100% fiber tear measured byrecognized industry in-process and post-production methods can beachieved with similar or less layer mass and polymer content. Thiseffect is possible at extrusion line speeds up to about 1300 FPM, usingsemi-crystalline mineralized resin blends with extrusion equipment dieand barrel zone temperatures from about 540° F. to about 615° F. Becauseof improved mineral thermal properties, oxidation of the extrudate uponexiting the die but before fiber contact improves about 10-50%, thusgreatly strengthening fiber bonding characteristics under normalequipment operating conditions.

Because of unique structural properties, mineral dispersions greatlyimprove the polymer-containing matrix thermal transfer and heatdiffusion properties. These characteristics provide outsizedimprovements on heat flow, heat seal activation temperatures, meltstrength, interfacial adhesion to fibers, interface bonding, hot tackstrength, heat seal layer crystallization, and cooling. Therefore, peelstrength upon fiber bonding during extrusion and heat seal issignificantly higher than neat polyolefins. The mineral-containinglayer's thermal and physical properties provide similar high-performancecharacteristics when heat sealed during packaging formation includingimproved and enhanced re-crystallization, heat tack, and molecularinter-facial entanglements. These improvements are observed using a widevariety of heat-sealing equipment that applies or transfers heat underpressure and time adjustments. Practical benefits include the reductionof plastic requirements during both heat seal to other surfaces andextrusion coating, for example, a polyethylene coated fiber surfacemight require from about 7.2 lbs/3 msf to about 20 lbs/3 msf coat weighton one or more sides for adequate fiber tear during extrusion andsufficient post-cooling peel strength during packaging formation.However, from about 20% to about 65% mineral-containing layer canimprove fiber bonding and heat seal characteristics with coat weightsfrom about 6.5 lbs/3 msf to about 12 lbs/3 msf and above. In many cases,an existing two side polyolefin-coated fiber composite can be extrusionbonded or heat sealed at similar or better performance using totalpolymer content on either one or both sides of the fiber-containinglayer up to about 40%-65% or less, reducing the resin cost per pound ofthe layer. Additionally, the mineral-containing composite layer is wellsuited for adhesion for medical packaging, although not limited tomedical related packaging, during radiation sterilization. Particularlyrelated to widely employed types of radiation such as gamma (cobalt 60particles) and electron beam (β particles). Electron beam is typicallyused for less dense materials from the shallower penetration depth ofthe lower energy β particles. Radiation sterilization does not requireporous packaging materials and is frequently the sterilization methodchosen when a barrier to gas penetration is a requirement of the medicaldevice.

However, radiation is frequently employed with permeable package typesif the packaging material properties will not be compromised duringtreatment. Stream autoclave sterilization requires high barrier, highermolecular weight, thermally stable materials, such as polypropylene orpolycarbonate, making mineralization of the mineral-containing compositelayer an excellent improvement in cost and performance, particularlywhen heat sealing peel strength are important factors in the packagingcharacteristics as well as reducing or eliminating the need for heatseal coatings. One standard used to measure heat seal strength includesASTM F88-94. Mineral-containing composite layers can be used to achieveheat seal strength in medical applications from about 0.5 to about 5 lbsper inch of seal width.

Also, due at least in part to the thermal characteristics of the mineralcontent, the mineral-containing layer mineralization can improve theavailable bonding sites and increase the internal cohesive splittingbetween polymer content of numerous sealable structures, e.g.,relatively incompatible materials, such as polyethylene and polybutylenelayers as a result of, among other things, improved interfacialadhesion.

Polymer melting is a key characteristic in the process. The reptationmodel has been widely used to explain the interdiffusion of polymersduring melting. The reptation theory can be used to model the motion ofan individual chain molecule during melting. According to the standardreputation theory, a polymer chain is confined to a tube that representsthe topological constraints arising from chain entanglements. Thethermal energy causes molecular movements to occur during melting. Withthe application of heat, the polymer molecules absorb heat energy andthe chain ends entangle. Upon mineralizing selected polymer layercomposites from about 20% to about 65%, the polymer chains diffuse morerapidly across the interface at wider temperature ranges and behavesimilar to higher molecular weight layers, weight high crystallinity,and less branching. Therefore, diffusing across the interface at widerranges of the interface temperatures, resulting in strong peel strengthheat seal results. In part, this strong seal is attributed to anincrease in entanglement density in the sealing area. The entanglementscan be considered to be a temporary intermolecular interaction betweenlong chain molecules, not preventing the material from flowing undershearing stress. For example, CaC0₃ particles facilitate polymercrystallization entropy with increasing percentage of weight and volumein the polymer, with cooling rates, as an example, from about 1.5 toabout 4.5° K/min, thus having impact on differential scanningcalorimetry (DSC) curves. Further, because mineral content acceleratesdiffusivity in the polymer melt, cooling times are truncated during theearly and later stages of the hot tack cycle, greatly improving earlyand subsequent extrusion and heat seal adhesion-T Dot Peel Strengthperformance. This effect is also seen during extrusion coating mineralloaded extrudates to fiber-containing surfaces. For example,Diffusivity=Thermal Conductivity (Specific Heat×Density), m²/sec=W(m°K+J(kg° K)×(kg/m³). This characteristic combined with thermal bulk alsolowers the requirement of polymer content in the mineral containinglayer up to 30-70% by weight of the layer. A further example includespolypropylene (PP) 40% filled by CaCO₃ would have heat diffusivity 3.5times greater than that of neat PP. This means it will take much lessthermal energy during the heat seal and extrusion coating process andalso the cooling time of the melt is reduced increasing hot tack anddelivering efficient and effective crystallization and interfacialbonding of the melt to fiber-containing and other type layers. Mineralloading of the polymer content can therefore decrease heating andcooling properties of neat or lightly filled (less than 20% by weight)polymer layers from about 1 to about 6 orders of magnitude dependingupon the polymer mix, type of minerals used, and rate of heat exposure.

Therefore, these mineral-enhanced entanglements can act as a topologicalbarrier to the movement of the polymer molecules. The entanglementprocess that occurs during the melting of polymer molecules has beenmodeled by considering entanglements as sliding contacts in a polymermatrix, showing that the elastic modulus in the rubbery state of melt isrelated to the entanglement density. Mineralization within the polymerlayers with specific gravities in the range of from about 1.19 to about1.62 g/cm³ alters the end state performance of these effects. Theaverage molecular weight between entanglements (Me) relates to the shearmodulus in the rubbery plateau region of the polymer (as observed in thegraph of log (shear stress) verses (log time)), Me is inversely relatedto the entanglement density, where T is absolute temperature, R is thegas constant, and D is the density. This equation is valid only for thepolymer in which chain entanglements are distributed homogeneously.

Among the processing parameters and considerations impactingmineralization of selected polymers for optimum adhesion to fibersduring extrusion of the mineral containing layer to the fiber-containinglayer as well as heat seal performance of the finishedmineral-containing packaging composite surfaces to other surfaces, bothpolymer and fibrous, during production of the packaging article,temperature plays an important role during heat sealing and duringextrusion coating. In many sealing applications, the heat flux must behigh enough to melt the polymer films. The energy required to achieve anoptimal seal, that is usually evaluated by seal strength, is dictated bythe material and thermal properties of the film in combination withnovel thermal and physical characteristics of the mineral contentcombining in part with the thickness of the mineral-containing layer,crystallinity, thermal diffusivity, melting point, contact resistance ofthe mineral-containing layer, etc.

The amorphous fraction of the polymer layer can be related totemperature and heat transfer, thus, mineralization can improve ultimatebonding strength. The energy required to achieve an optimal seal, thatis usually evaluated by seal strength, in part is dictated by thematerial and thermal properties of the polymer layer once modifiedthrough mineralization, including thickness, crystallinity, thermaldiffusivity, heat conductivity, heat capacity, melting point, contactresistance, etc. The maximum heat seal strength occurs when temperaturecompletely melts crystalline regions of the polymer films. The mineralparticle content thermal properties accelerates crystalline melt andalso shortens hot tack intervals achieving maximum precooling peelstrength.

The strength of all heat seals formed by hot die sealing behaves inbroadly the same way, e.g., the hot seal is initially relatively weak atthe conclusion of the heat seal cycle, however, as the seal cools itgains strength at very high speeds. In seconds or less, the seal reachesambient temperature and its terminal strength. The term “hot tack”refers to the strength of the hot seal during approximately the first500 to 1,000 milliseconds after peak heat application to sealedsurfaces. Thus, hot tack is measured prior to hardening orrecrystallization of the sealant polymers. The seal itself changesstrength rapidly during the cooling process, starting at millisecondzero. Hot tack is a variable that is a function of both time and ambientcooling conditions, thus affecting heat transfer from the seal to thesurrounding environment.

Thermal aspects of the sealed surfaces including heat capacity, rate ofheat transfer, and rate of crystallization, are critical to forming afunctional seal with adequate peel strength and fiber tear. Hot tackperformance can be described by a curve of seal strength vs. sealtemperature or, otherwise stated, the cooling curve of the material. Thecurve of hot seal strength vs. cooling time portrays the tack behaviorof a material graphically. Mineralized polymers can improveself-adhesion above the melt temperature due to the thermal attributesof the mineral content, both in heterogeneous and homogeneous ethylenecopolymers. Also, mineralization can provide superior performancewithout the need for extensive surface separation of the lower molecularweight and higher branch content. Improved self-adhesion in the melt dueto advanced thermal kinetics of about 20% to 65% mineralized layersimprove the ultimate adhesion and peel strength of the heat seal bond aswell as bonding efficiencies during the machining process as the meltcools. Normally, these characteristics are highly dependent uponbranching, however, mineralization can extend high performance tackalong a wider range of poly dispersed and heterogeneous materialsthrough improved inter-diffusion rates among a more dispersed range ofpolymer densities. These advantages are also notable when extrudingvarious polymeric blends during extrudate heating and contact andbinding to fibers, resulting in improved tack, adhesion, and thesubsequent heat-sealing process when forming the packaging article(s).Molecular weight ranges of the polymer bonding agent content of themineral-containing layer from about Mw 10,000 to about 100,000. Further,having, but not limited to, a minimum of about 10%-70% of the polymercontent having branching index (g′) of about 0.99 or less measured atthe Z-average molecular (Mz) of the polymer. Some part or all of themineral-containing layer polymer bonding agent is preferred but notrequired to a have an isotactic run length from about 1 to about 40.Further, the mineral containing layer polymer bonding content shear raterange is from about 1-10,000 at temperatures from about 180° C. to about410° C. The mineral-containing composite layer, having mineral contentfrom about 20% to about 65% (but not limited to), can generally providehot tack operating ranges from about 25° C. to about 225° C. having fromabout 1.0 N/mm to about 6.0 N/mm seal strengths. Using polyethylenecopolymers, with temperatures from about 80° C. to about 220° C. andhaving hot tack strength from about 2.5 N/mm to about 15 N/mm withoptimal strength in the range of about 120° C. to about 160° C.Additionally, mineral-containing dispersed and non-interspersed polymerlayer peel strengths having ranges represented in J/m2 from about 1 toabout 45, having sealing (dwell) times in the range from about 0.30seconds to about 15 seconds, in temperature ranges from about 115° C. toabout 240° C. with corresponding seal pressures at or below about 0.80MPa.

Further, extrusion coated mineral-containing resins can be bondedsubstantially and continuously with excellent fiber tear in time framesfrom about 0.01 seconds to about 6.0 seconds, with an initial extrudatecontact time of from about 250 to about 2,500 milliseconds andtemperature ranges from about 490° F. to approximately 635° F., atcontact pressure. Embodiments of the present bonded mineral-containinglayer, at the point of post crystallization and beyond the rubbery zone,have a Dot T-Peel strength measured by ASTM D 1876 of from about 5 toabout 450 J/m² up to 75% to 100% fiber tear observed within the damageand fracture zone. Results using 20% to 70% (by weight)mineral-containing extrudate were from about 0.5 lbs per thousand squarefeet (msf) to about 20 lbs per msf. The low polymer mass requirementsresulted in part to mineralizing low molecular weight polymers havingsome amorphous polymer structure at the layer interface. Since sealstrength curves for most materials are generally of the same shape, anindex number related to the rate of the increase of seal strength withcooling can be used if the cooling-time curve is followed to the pointof ambient temperature, and then leveling off at the terminal sealstrength. The terminal seal strength is measured by the peel test on atensile machine. This measurement can be taken minutes, hours, or daysafter ambient temperature is reached. Prior to measurement, the sealpressure is preferably sufficient to flatten the tested sample to thepoint at which maximum molecular contact is made between the twosurfaces, as heat sealing and extrusion coating extrudates to fiberinvolves diffusion of chain ends from each surface into each other.

Also, sufficient dwell time is preferably allowed to permit theinterface to reach the known temperature of the heat-sealing method. Forcoating and films up to about 3.0 mils, 100-250 milliseconds (ms) issufficient. During production, for efficiency, short dwell time isadvantageous. Therefore, enough heat is preferably applied, and tack ispreferably present as soon as possible to keep the initial packageintegrity sufficient enough to maintain a seal as the cooling processcontinues.

High mineral content provides very fast thermal conductivity anddiffusion. Thus, tack is formed more quickly and with higher strength.Also, the optimum heat threshold is achieved sooner, e.g.,crystallization temperature, further offering faster heat seal integrityduring the production process. The ability of an adhesive or polymercoating layer to resist creep of the seal while it is still warm or in amolten state is called hot tack. Hot tack includes two components, themelt strength of the seal layer at the temperature of the seal, and theinterfacial adhesion of the sealant layer. Table 8, below, illustratesthe heat seal tack improvement of mineralized resins according to thepresent embodiments (Film A) vs. neat polyolefins (Film B).

TABLE 8 Hot Tack Performance (ASTM F-1921) Interface Observations-N/25mm Std. Temperature @250 MS Mean Dev. N FILM A: 20%-40% Mineralized,20%-60% Amorphous, 20%-55% Crystalline Structure 105 0.19 0.16 0.22 0.190.03 110 1.68 1.68 1.68 1.68 0.0 115 2.25 2.25 2.31 2.27 0.03 120 1.951.76 1.63 1.78 0.16 125 0.95 1.25 1.17 1.12 0.16 FILM B: 100% Neat, NoMineral Load 105 0.19 0.19 0.22 0.20 0.02 110 0.76 0.79 0.62 0.72 0.09115 1.19 1.49 1.49 1.39 0.17 120 0.54 0.43 0.52 0.50 0.06 125 0.46 0.410.65 0.51 0.13 Note: Mineralized resin density is 1.20 to 1.35 g/cm³

At an interface of from about 155° C. to 120° C., mineralization isprojected to improve the performance from about 15% to about 70%.

Heat sealing of a polymer is a combination of mass and heat transferprocesses. Heat flow to the polymer films, the melting of the polymer,and the inter-diffusion of molten polymer chains are time relevant. Inorder to form a strong, intact seal, an adequate dwell time, or theduration of time when the films make contact together during sealing,must be given to allow the mass and heat transfer processes to proceeduntil the target end conditions are reached, e.g., complete melting ofcrystalline fraction to obtain crystal fusion using, for example, randomcopolymers with densities at or above 0.88 g/cm³ and adequateinter-diffusion of molten polymers to form a continuum interface.Potential, but not limited to, copolymer isotacticity index from about20% to about 85% measured by the DSC method can be used, and as suchmineral-containing layers with mineral by weight concentrations up toabout 75% having a melt flow index “MFI” from about 190 g/10 minutes toabout 1.0 g/10 minutes measured by the NFT 51-620 standard can beobtained. The addition of polyolefin plastomers and elastomers havingthe densities per ASTM D 792 from about 0.86 to about 0.891 g/cm³ withDSC melting peaks from about 59° C. to about 110° C. can be consideredhaving a 2% secant modulus, and MPa from about 15 to about 120. Theoptimal dwell time interacts strongly with temperature; the applicationof higher temperatures reduces the time required for polymer layers andvice versa. Mineralization alters the specific heat of the mineralizedpolymer layer, thermal diffusion, and heat conductivity. Therefore, uponheat capacity apex, dwell time and pressure requirements cansignificantly diminish. At the same time, a high-performance bond takesplace along the fiber-containing layer contact surface. For example,increasing the dwell time from 0.3 to 1.4 s at a 130° C. temperatureduring heat sealing 12 lbs/3 msf layer of PE increased seal strength byonly 10%. However, a 25% to 65% mineralized polyolefin layer increasedpeel strength from about 20-30% with dwell times of about 0.4 to 0.9seconds with a 9 lbs/3 msf layer weight. Therefore, dwell time duringheat seal can contract, however, it is still considered to be asecondary factor compared to temperature. High temperature sealingmethods can be employed such as hot air with seal temperatures fromabout 650° C. to about 1200° C. having nominal seal pressures belowabout 30 psi and dwell times of below about 2 seconds. Molecular contactbetween two surfaces is necessary in order to allow the diffusion ofpolymer chains across the seal or contact interface. Pressure applied tomineral-containing layers during the sealing process can be from about 5psi to about 90 psi. This contact can be established by compressing thepolymer films together or to fiber surfaces, under compression pressure.The applied pressure helps to remove surface irregularities and toincrease the actual contact area between the sealed surface interface,thereby increasing heat flow. However, the mineralized layer can providegreater heat flow efficiencies, thus reducing dependence on pressure.The plateau initiation temperature is when the interface temperature ishigh enough to melt the crystalline region of the polymer completely.Other than pressure required to accomplish efficient surface areacontact between the sealing surfaces, the effect of pressure on heatsealing can be considered a less important variable when usingmineralized layers vs. polyolefin layers. Mineralization improves thecritical inter-diffusion process of polymer molecules.

The interface temperature between the two sealing surfaces plays animportant role governing the seal initiation temperature. The sealinitiation temperature is dependent on the amorphous fraction of thepolymer. For example, the seal initiation temperature for polyethyleneis determined when the amorphous fraction reaches about 60-85%. However,because of mineral particle thermal properties, the amorphous fractioncan be extended to about 40% to about 85%. The plateau initiationtemperature is determined to be when the interface temperature is highenough to melt the crystalline region of the polymer completely.

For example, reviewing the heat sealability of mineral-containing layersbonded to fiber-containing layers provides failure modes including:peeling, delamination, and tearing. The peeling mode is when the sealingtemperature is lower than the melting point of the polymers. Whencombining the peeling and delaminating failure modes, the interfacetemperature is below the final melting point of the polymer, resultingin incomplete melting of crystallites. However, mineralization helpsimprove performance through stabilization of the interface layer duringtemperature changes. When the interface temperature reaches the plateauinitiation temperature, the seal strength increases, and delaminating ortearing failure modes or a combination of these phenomena are commonlyobserved. The delaminating failure mode occurs due to the weak bondingbetween the laminate layers.

The peeling failure mode is generally correlated with low heat sealstrength due to low entanglement density in the sealing areas, whiletearing mode or fiber tear is associated with the highest seal strength.In the latter failure mode, the strength of the seal is higher than thecohesive strength of the polymer indicating production of an ideal sealand adhesion. The heat seal failure mode is dependent on the materialtype, laminate structure, and the surface properties of the sealsubstrate. For instance, two failure modes during heat sealing is anexample, namely fractures in the seal and at the edge of the seal, andnecking behavior at the edge of the seal related to the peeling failuremode. Corona discharge treatment, which is commonly applied to increasesurface activity of polymer films to improve printability, can createcross-links on the film surface that reduce the inter-diffusion ofpolymer chains, thereby changing the failure mode of the material. Theobserved difference due to the reduction in entanglement density in thesealing area is caused by the corona discharge treatment. However,particle mineralization of the polyolefin can reduce or mitigate theadverse effect of corona treat to the surface of the mineral-containinglayer.

In general, heat transfer can be defined as a transfer of heat energydue to the presence of a temperature gradient in a medium, causing thetransfer of heat energy from high to low temperature. Conduction heattransfer is the main mode of heat transfer involved in heat sealing.Conduction heat transfer occurs when more energetic molecules that areat a higher temperature share their energy with less energetic moleculesin a stationary medium. Conduction of heat through a medium involvescollision and diffusion of the molecules during their random motion,vibration of molecules, and/or transport of thermal energy through freeelectrons. Collision and diffusion of molecules predominantly occur ingases and liquid media, whereas vibration of molecules and movements offree electrons are the main heat transfer mechanisms that occur insolids. Heat transfer during heat sealing of thin profile film, coating,and fiber materials is approximately one-dimensional. The rate equationfor plane geometry can then be used: q=−K(dT/dx), where q is the neatflux (W/m²), which is the heat transfer rate in the x-direction per unitarea perpendicular to the direction of transfer, and dT/dx.

is the temperature gradient in the x-direction, and K (W/m° K) is thethermal conductivity that characterizes the heat transport property of agiven material. As explained, mineralization of the polymeric matriximpacts the layer's K value, and thus when mineral-containing polymerfilms are clamped together with heated seal jaws, the conduction of heatfrom the surface into the film medium will result in transient alteredheat transfer vs. polyolefins. The temperature of the mineralized filmincreases with differing time along the temperature gradient. In mosttransient heat conduction problems, the temperature is dependent on bothtime and the position along the direction of the medium. Themathematical equations that explain the thermal conditions at theboundaries of a system are called boundary conditions. Mineralized layerboundary conditions result in far superior heat seal attributes. Inreality, since the film-film or polymer-fiber interface does not haveperfect contact between surfaces due to the presence of micro-gaps,resistance to heat flow will need to be taken into account during heattransfer modeling analysis. When thermal energy is transferred acrossthe interface by conduction through the contact faces, and through theinterstitial pockets of air (or liquid contaminant) present in themicro-gap. The heat transfer across an interface can be explainedaccording to Newton's law of cooling, applicability in real experimentalconditions. These assumptions involved surface roughness or smoothness,different contact geometry such as small slopes or curved shapes, and soon.

Seal integrity can be defined as a seal that is continuous andconsistent without having any discontinuities, such as micro-leaks, orany other defects such as wrinkles, abrasions, dents, blisters, anddelamination. Seal integrity is important in food packaging to ensurethat the product is protected from unwanted factors from the atmosphere,such water vapor, that are deleterious to sensitive components in food.Seal integrity and seal strength are the main parameters that determinethe quality of a heat seal. Seal integrity is defined as a sealcontinuum in which there is a complete fusion of the polymer with nodiscontinuities. The maximum seal strength can be defined as the maximumforce per unit width of seal required to separate progressively theseal, under some specific test conditions. In many food packagingapplications, adequate seal strength is critical during productdistribution to ensure that the package can withstand mechanicalstresses because of handling. Accordingly, seal strength is often usedas one of the process control parameters to ensure that adequate sealintegrity is achieved. The dominant process variables that dictate sealstrength are jaw temperature, jaw configuration, and dwell time (thetime spent in the seal cycle when polymer films are held together by theseal). Higher peel seal strength was reported using linear low-densitypolypropylene (LLDPE) samples of less branched and higher molecularweight. Also, reported seal strength of a semi-crystalline polyolefinwas closely related to the melting temperature. Upon polyolefinmineralization, the melt temperature of the polymer content remains thesame. However, the mineral content improves the performance of lesscrystalline structures through more efficient heat conductivity anddiffusion characteristics.

Seal strength properties can also be affected by surface treatment andmodification of polymer films. In general, homopolymers require lesscontact time to achieve the maximum seal strength than polymerscontaining structurally different (heterogeneous) copolymers.Mineralization from about 20% to about 65% altered those dynamics due tothe changed thermal properties of the matrix, particularly entanglementat the interface layer. For example, samples sealed at the jawtemperatures (150° C. and 165° C.) at 1.5 seconds dwell time found thatmineralization decreased dwell time. Also, slightly increasing jawtemperature further improved dwell times and significantly improved sealpeel strength from about 10% to about 30%. Under this high temperaturelong seal time seal condition, interface temperatures ranged from about130° C. to about 150° C. These results suggest that long contact timeresults can be improved when sealing at higher jaw temperatures toprevent excessive squeeze out of polymer melt, and possible materialdegradation, whereas at lower jaw temperatures, the dwell time is stillsufficient to allow for the melting of crystallites and diffusion ofpolymer chains across the interface to form a strong seal. Examplemineral containing layer weights are from about 7.5 lbs/3 msf to about60 lbs/3 msf, having heat seal strengths from about 1.25 lbs/in and toabout 6.45 lbs/in, and terminal hot tack strength from about 2.10 toabout 8.55 N/in. Heat seal initiation temperatures from about 59° C. toabout 76° C. and hot tack initiation temperatures from about 57° C. toabout 99° C. Pressure during dwell from about 10 psi to about 80 psi anddwell times from about 0.30 seconds to about 1.75 seconds.

Further, low temperature seals from about 340° C. to about 425° C. atdwell time intervals of about 0.50 to about 6.25 seconds with sealpressures from about 20 psi to about 85 psi have average peel force fromabout 0.50 to about 4.0 lbs lbs/inch. Heat seal process methods that canalso be used include tray sealers, transverse form-fill-seal, platendie, and rotary 4-side machines.

Within the cube and block particle class, above, particle surface areais an important filler property. For example, many effects aresurface-to-area dependent and can impact polar polymers. Polarcharacteristics can have an impact on surface tension and surface energylevels. The preferred, but not limited to, average particle surface areawithin the composite is from about 1-1.3 m²/g to about 1.8-2.3 m²/g.Further, preferred particle types having the average surface particlesurface area include the calcites group, of which aragonite, calciumcarbonate, dolomite, anhydrite, and barite are included. Mineral fillersused have a very positive effect on pre- and post-extrusion conditioningmethods used to improve adhesion and the surface performance of apolymer layer. Calcium carbonate particles have been found to beparticularly useful, including particles having about 18-80% particlediameters finer than 6 μm and about 33-96% particle diameters less than10 μm. Other preferred, but not limited to, particle characteristics ofCaCO₃ are shown in Table 9, below.

TABLE 9 Particle characteristics of CaCO3 Particle Coating Fatty AcidsIncluding Stearates Hunter Reflectance (Green) 91-97% Hunter Reflectance(Blue) 89-96% Mohs Hardness 2.75-4.0 pH in Water, 5% Slurry, 23º C.8.5-10.5 Resistance in Water, ohms, 23º C. 5,000-25,000 ASTM Dl 199 Max% on 325 Mesh 0.05-0.5 Volμme Resistivity @ 20º C. 109-1011 ohms pH8.5-10.5 Standard Heat of Formation, CaCO3 288.45-288.49 Kg-cal/molefrom its Elements @ 25º C. Standard Free Energy of Formation,269.53-269.78 Kg-cal/mole CaCO3 from its Elements Specific Heat (betweenO to 100º C.) 0.200-0.214 Heat Conductivity 0.0071 g · cal/sec · cm² · 1cm thick 20º C. Coefficient of Linear Expansion C = 9 × 10-6 @ 25 to100º C. C = 11.7 × 10 (m 25 to 100º C.

Also, nano-cellulose can be used in the mineral containing compositelayer having a crystalline content from about 40%-70%, includingnano-fibrils, micro-fibrils, and nanofibril bundles, having lateraldimensions from about 0.4-30 nanometers (nm) to several microns, andhighly crystalline nano-whiskers from about 100 to 1000 nanometers.Nanocellulose fiber widths are from about 3-5 nm and from about 5-15 nm,having charge densities from about 0.5 meq/g to about 1.5 meq/g, withthe nano-cellulose having a stiffness from about an order of 140-220 GPaand tensile strength from about 400-600 MPa.

Most pure inorganic matter, including salts, has very high surfaceenergy as measured by surface tension, e.g., up to and over 200dynes/cm, due to the imbalance of bonding forces at the surface. Highsurface-free-energy materials are generally hydrophilic and absorb waterfrom hydrogas of the atmosphere, corresponding reducing the energy levelbased on the rule that all matter tends to assume its lowest energy,most stable state. Observed surface tensions on all high surface energymineralized layers between 95% and 0.6% relative humidity are found tobe pretreatment levels from about 34 dyne/cm to about 45 dyne/cm,respectively. In comparison, unfilled (neat) LDPE has an approximate 32dynes/cm. As particle size decreases, surface activity increases. Smallto very small particles have little mass, low bulk densities, and areaffected by forces of agglomeration. The forces may be mechanicallyeffective over great distances relative to molecular dimensions. Theseforces greatly improve adhesion to fibers of the composite duringextrusion coating production. Also, the enhanced surface energy levels(dyne) greatly improve surface performance for ink and mineralcontaining layer composite surface adhesive applications.

Further, this composite surface performance is magnified when exposed totreatments found on extrusion coating lines to enhance neat polyolefin(unfilled) layers. The type of treatment largely depends upon the typeof substrate to be extrusion coated. In flame treatment, which isprimarily used for heavy paper and paperboard, the fiber substrate islightly oxidized to enhance its adhesion to the polyolefin. The flametemperature is in the range of about 1500-2100° C. The term polyolefinencompasses all those polymers produced by an olefin as a startingmonomer, whose general formula is C_(n)H_(2n). Most common polyolefinsin the packaging field are polyethylene (PE) and polypropylene (PP).Although they have different specific properties, both polymers areinherently hydrophobic, which is in turn responsible for their typicallypoor wet-ability, especially to waterborne adhesive and printingsystems. For this reason, polyolefins generally need to besurface-activated before the deposition of inks, paints, adhesives,metals, and coatings. Flame treatment is a valuable technique to improvethe surface energy of neat polyolefins. However, because calcite fillersare generally very hydrophilic and the filler provides advanced surfaceenergy, the net result of flame treating is enhanced, resulting insuperior performance. Further, flame pre-heating paper during theextrusion coating process generates oxidation prior to fiber extrudatecontact, improving adhesion. It also heats the paper, removing moisture.The polyolefin extrudate mineral-containing process temperature at fibercontact is elevated, normally between 530° F. and 630° F. Therefore,very little moisture or water is present. Under low moisture and waterconditions, 20% to 60% mineral-containing polyolefin has very highresident surface energy levels. These elevated levels (about 45-100dynes/cm) provide for good fiber polyolefin adhesion and fiber tearduring heat sealing, water based, and hot melt glue processes when themineral-containing layer makes contact with opposing polymer orfiber-containing layers. Flame treatment is simple in design, easy tooperate and relatively inexpensive. Plasma treatment to the surface ofpolypropylene (PP), polyethylene (PE), high-density polyethylene (HDPE),EPDM, and other polyolefin-coated surfaces, is frequently used becauseof the low resident surface energy found on polyolefin coatings, oftenbetween 28-36 dynes/cm² (mJ/m²). For example, expressed in mN/m, theapproximate surface energy levels of various materials are: PTFE-20,silicone-20, PP-30, PE-32, PS-34, PC-34, ABS-34, XLPE-32, PUR-34, UVink-up to 56, water-based coating up to 56, UV-glue up to 50,water-based glue. However, 40% to 60% mineralized layers beforedemonstrate up to 40% improved dyne levels. Generally, polyolefins with“low surface energy” or “non-polar surfaces” provide poor conditions foradhesives, gluing, or adhesion, thus resulting in poor quality inkwet-ability and graphics and very poor bond strength between theadhesive and its opposing surfaces. Ink wet-ability being defined as thesurface tension or surface energy of the solid substrate in relation tothe surface tension of the liquid, the better the wet-ability, thesmaller the contact angle. The problem is aggravated when using UVcuring or water-based adhesives, inks, and coatings. The strength ofattraction between a material and a coating is determined by therelative surface energy and surface tension of the materials. The higherthe solid's surface energy relative to the liquid's surface tension, thegreater the molecular attraction. This draws the ink or adhesive closerfor high bond strength. The lower the solid's surface energy relative tothe liquid's surface tension, the weaker the attractive forces and thecoating will be repelled. Plasma- and corona-treated on nontreatedpolymer-containing layers having mineral content from about 20% to about70% can exceed the contacting liquid's surface energy from about 1-15mN/m. The challenge faced when extrusion coating polyolefins and likepolymers is to increase the surface energy (polarity) of the material toa level significantly higher than that of the opposing surface tensionof the ink, coating, or adhesive, such that the surface providesfavorable wetting and adhesion. Typically, the surface energy of thesubstrate needs to exceed the surface tension of the ink, paint,coating, or adhesive from about 10-15 dynes/cm² (mJ/m²).

There are several methods of increasing the surface energy and polarityof plastics. These include harsh, potentially environmentally harmfulwet chemical treatments, high temperature flame torch treatments, highvoltage corona treatment, and plasma surface activation. Plasma surfaceactivation, which exposes low-surface-energy extrusion-coatedpolyolefins to the highly active environment of either vacuum oratmospheric plasma, is a very effective and long-lasting method ofincreasing their surface energy and polarity.

Corona treatment of plastic substrates involves high voltage andfrequency electricity discharged from an electrode into an ionizing airgap (generally about 0.060″), where it passes through the substrate toan electrically grounded metal roll. This treatment increases thesurface tension (measured in dynes/cm) of the substrate to at least 10dynes/cm higher than the tension of the extrusion coating.

However, in higher mineral loadings from about 20%-70% mineral contentby weight, because of significant particle exposure, the post-extrusionsurface of the mineral polymer composite generally has significantlyimproved onset energy levels across the surface of the composite. Uponpost-corona or plasma treatment commonly used during extrusion coatingprocesses, the mineral reacts more favorably and obtains significantlybetter post-treat energy levels than solely polymeric surfaces. Table10, below, illustrates comparative estimated values of dyne levelsbefore and after corona and plasma treatment of the polymer composite byweight of filler added. Results can vary up to ±25% depending uponmineral selected and process variables. Without posttreatment, theorganic dyne level of a mineral-filled polymer (from about 20% filled upto about 70% filled) can be improved from about 10% to about 30%.

TABLE 10 Surface Energy Mineral-Containing Layer Values No Post- PolymerTreatment Post-Treated 10-20% 30-40% 40-70% Polypropylene 20 Dyne 29-36+5% +30% +50% Polyethylene 32 Dyne 39-42 +2% +45% +50% Polystyrene 34Dyne 39-44 +2% +30%

The mineral-containing interspersed or non-interspersed polymercomposite layer can be substantially and continuously directly bonded toa fiber surface or to the fiber surface interface adhesive layer usingextrusion coating or extrusion lamination. Further, the fiber-containinglayer can contain inorganic mineral coatings and fillers, e.g., clay,kaolin, CaCO3, mica, silica, TiO2 and other pigments, etc. Othermaterials found in the fiber-containing layer include vinyl andpolymeric fillers and surface treatments such as starch and latex.Preferred characteristics of the fiber-containing layer bound to themineral-containing layer include, but are not limited to, a smoothnessrange of about 150 to about 200 Bekk seconds, and an ash content fromabout 1% to about 40% by weight. Also, in this example, the fibercontaining layer coefficient of static friction, μ, is from about 0.02to about 0.50. Identified cellulose within the fiber-containing layerpreferably has a thermal conductivity from about 0.034 to about 0.05W/m·K. If using air-laid paper or non-woven fibers, the fiber content ispreferably from about 40% to about 65% of the layer by weight. Otherpreferred, but not limiting, characteristics of the fiber-containinglayer are shown in Table 11, below.

TABLE 11 Fiber Layer Characteristics Fiber Aspect Ratio (Average) 5-100Fiber Thickness (Softwood) 1.5-30 mm Fiber Thickness (Hardwood) 0.5-30mm Filled Fiber Content 1% to 30% Fiber Density 0.3-0. 7 g/cm² FiberDiameter 16-42 microns Fiber Coarseness 16-42 mg/100 m Fiber Pulp TypesMechanical, Thermo-Mechanical, Chemi- (Single-to Triple-Layered)Thermo-Mechanical, and Chemical Permeability 0.1-110 m² × 10¹⁵ HydrogenIon Concentration 4.5-10 Tear Strength (TAPPI ® 496, 402) 56-250 TearResistance (TAPPI ® 414) m 49-250 Moisture Content 2%-18% by Weight

Coextrusion methods provide the possibility for non-interspersed contactlayers within the mineral-containing layer. Based on performance andstructural requirements, the finished composite structures can containseparate layers in the composite that can vary based on the type ofmineral and amount of mineral content per layer, degrees of amorphousand crystalline content per layer, and type of polymer resin and resinmixes per layer. The more extruders feeding a common die assembly, themore layered options become available to the non-interspersedmineral-containing layer. The number of extruders depends on the numberof different materials comprising the coextruded film. For example, anon-interspersed mineral-containing composite may comprise a three-layerto six-layer coextrusion including a barrier material core that couldbe, for example, a high-density polyethylene and low-densitypolyethylene mix having a 25% to 65% mineral content by weight in thefirst base layer, this layer making contact with the fiber surface.Subsequent layers may contain differing mineral contents, neat LDPE, orpolypropylene. Another example is a six layer coextrusion including abottom layer of LDPE, a tie-layer resin, a 20% to 65% mineral-containingpolypropylene barrier resin, a tie-layer, and an EVA copolymer layer,and a final layer of polyester. Tie-layers often are used in thecoextrusion coating of multiple layer constructions wheremineral-containing polymers or other resins would not bond otherwise,and tie-layers are applied between layers of these materials to enabledesired adhesion. Another example multilayer film construction is25%-65% mineral content LLDPE/tie-layer/EVOH barrier/tie-layer/EVA.Interspersed, e.g., monolayer, and noninterspersed, e.g., multilayer,coextrusions can comprise from one to six layers of themineral-containing layer substantially and continuously bonded acrossthe surface of a fiber containing layer. Layers can be designed toimprove hot tack, heat-sealability, seal activation temperature, andextrudate adhesion to fiber, mineral enhancement of barrier performance,surface energy, hot and cold glue adhesion improvements, etc.

Table 12, below, shows example layer constructions (not limited to)found in the mineral-containing resin and extrusion coated or laminatecomposite structure. The preferred single layer ranges contain fromabout 0% to about 65% by weight mineral content, from 25%-80% amorphousto 25%-80% crystalline structure by weight, and 25%-65% cellulose,nano-cellulose, or nano-minerals by weight. Also, the mineral content ofthe mineral-containing layer(s) may comprise different fillers withdifferent densities, size, and shape depending upon the desired outcomeof the final composite structure.

TABLE 12 Examples of Non-Interspersed (Multilayered) Mineral CompositeLayers Layer Structure Example 1 Example 2 Example 3 Example 4 Example 5Example 6 Mono- LDPE HDPE LDPE-HDPE LDPE-MMW LLDPE- PLA-bio layer (1)resin blend HDPE resin LDPE resin derived blend blend starch- basedresin blend Mono- Bio-derived, LDPE-bio LDPE-LLDPE- LDPE-HDPE- PP-bioULDPE- layer (2) starch polymer derived starch bio derived LLDPE-blendderived HDPE-bio blend polymer blend starch blend starch-based derivedpolymer blend starch polymer blend 3-Layer HDPE-LDPE HDPE-PP HDPE-PETLDPE-PP LLDPE-PET EVA- LDPE 4-Layer EVA-ethylene HDPE-EVA- BiaxiallyOriented EVA-PE- PVC-ABS- vinyl acetate Ionomer resin- oriented homo-polypropylene- MMWHDPE PC Nylon EEA-ethylene Polyamides- poly-propylene-HDPE-PE- oriented acrylic acid- polyester- metallized PET polypropyleneHDPE-EAA polypropylene- ethylene acrylic PE acid

Additional downstream product applications for monolayer and multilayermineral-containing layers bonded to fiber-containing layers include, butare not limited to, coated Tyvek® and Tyvek® trays, coated paper forform-fillseal, peelable films, and direct seal labels.

In some cases, the mineral-containing layer can be designed as a waveblocker, including UV. Using mineral content from about 15% to about 65%can block various waves within the wave spectrum from about 10% to about100% if the layer is from about 2.5 lbs/3 msf to about 150 lbs/3 msftotal layer weight. The sum of all the layers in the mineral-containingcomposite can obstruct some waves as shown below in Table 13, below.

TABLE 13 Wavelength Classes Class Frequency Wavelength EI Y 300 EHz  1pm 1 HX  30 EHz  10 pm 1 Sx  3 EHz 100 pm 1 EUV 300 PHz  1 nm 1 NIR  30PHz  10 nm 1 MIR  3 PHz 100 nm 1 FIR 300 THz  1 μm 1 EHF  30 THz  10 μm1 SHF  3 THz 100 μm 1 UHF 300 GHz  1 mm 1 VHF  30 GHz  1 cm 1 HF  3 GHZ 1 dm 1 MF 300 MHZ  1 m 1 LF  30 MHz  10 m 1  3 MHz 100 m 1 300 kHz  1km 1  30 kHz  10 km 1

Additionally, if relative clarity is desired in the mineral-containingcomposite layer the following resins are possible, but not limiting,bonding agents for these materials: carboxy-polymethylene, polyacrylicacid polymers and copolymers, hydroxypropyl cellulose, cellulose ethers,salts for poly(methyl vinyl ether-co-maleic anhydride), amorphous nylon,polyvinylchloride, polymethyl pentene, methylmethacrylate-acrylonitrile-butadiene-styrene, acrylonitrile styrene,polycarbonate, polystyrene, polymethyl acrylate, polyvinyl pyrrolidone,poly (vinylpyrrolidone-co-vinyl acetate), polyesters, perylene,polyethylene naphthalate, ethylene vinyl alcohol, and polylactic acidscontaining from about 10% to 65% mineral content. Variousmineral-containing layer polymer and mineral content can be determinedbased upon performance and content requirements considering theparameters shown in Tables 1-21, above. Branched, highly branched andlinear polymer combinations are possible in all composite layerconstructions. Examples are shown in Table 20 (not limited tocombinations within the table) of the interspersed and non-interspersedmineral-containing layer constructions, not including tie layers. Layercombinations depending on coextrusion die design, flow properties, andprocessing temperature allowing for coextrusion fusion layers and/orsubsequently extrusion laminating or laminating the layers into thefinal mineral-containing composition of which individual(non-interspersed) or total combination of layers having by weightmineral content of about 20-65%. Layers can be uniaxially or biaxiallyoriented (including stretching) from about 1.2 to about 7 times in themachine direction (MD) and from about 5 to about 10 times in thetransverse direction and stretched from about 10% to about 75% in boththe (MD) and (CD) directions. Generally, although not limited to,polyolefin mineral content bonding agents have number average molecularweight distributions (Mn) of from about 5,500 to about 13,000, weightaverage molecular weight (Mw) of from about 170,000 to about 490,000,and Z average molecular (Mz) of from about 170,000 to about 450,000.Contained within the mineral-containing composite mono-layer ormultilayer (dispersed or non-interspersed) structure may differ inmolecular weight, density, melt index, and or polydispersity index. Thepolydispersity index being the weight average molecular weight (Mw)divided by the number average molecular weight (Mn). For example only,and without limitation, the mineral-containing layer may have a Mw/Mnratio of from about 6.50 to about 9.50. Using wet or dry ground CaCO₃ asan example, it can be surface treated at levels from about 1.6 to about3.5 mg surface agent/m² of CaCO₃. The surface treatment can be appliedbefore, during, or after grinding. Mean particle sizes range from about,but not limited to, 0.7 to about 2.5 microns, having a top cut fromabout d98 of 4-15 microns, and a surface area of from about 3.3 to about10.0 m²/g. For improved dispersion into the polyolefin bonding agent,the CaCO₃ mineral content can be coated with fatty acids from between,but not limited to, about 8 to about 24 carbon atoms.

The preferred surface treatment range is about 0.6 to about 1.5% byweight of treatment agent or about 90-99% by weight of CaCO₃ Polyolefinbonding agents having lower molecular weights and high melt indexprovide improved downstream moisture barrier characteristics.

Brightness is the reflectivity of naturally colored pulps, and of paperand board made from such pulp, to light in the blue portion of thespectrum. As such, brightness is defined as the reflectivity ofnaturally colored pulp, paper, boards woven, synthetic, and non-wovenfiber-containing layers, at an effective wavelength of 457 nm. Light ofthis wavelength appears blue to the human eye. Brightness is animportant appearance property of paper not only because of its aestheticvalue, but also because of its effect on legibility and contrast betweenprint and paper. Brightness should not be confused with “whiteness.” Thedegree of whiteness of a paper conveys information on its colorneutrality. Two widely accepted methods of brightness measurement are GEbrightness, chiefly employed in the United States, and ISO brightness,widely used in other countries, especially in Europe. The TAPPI®standards describing these methods are T 452 for GE brightness and T 525for ISO brightness.

When applied to a fiber-containing layer, the present mineral-containinglayer(s) can substantially improve the brightness of thefiber-containing layer when the fiber layer has from about 40 to about90 GE brightness. Depending upon desired results, the mineral-containinglayer can employ a variety of mineral selections and be both dispersedand non-dispersed. Particles can vary in size, shape, and type. Themineral composite mineral-containing layer can vary in weights fromabout 8 lbs/3 msf to about 50 lbs/3 msf with thicknesses from about 0.5mil to about 5 mil, and individual layer or combined layer weightedaverage densities from about 0.91 g/cm³ to about 1.55 g/cm³. Dependingupon the nature and existing brightness of the fiber-containing layer,the fiber-containing layer can have improved brightness from about 10%to about 250%. For example, the fiber-containing layer with a brightnessof 40 could be improved to a brightness level of about 100.

Opacity is related to the ability of light to pass through paper. TheTAPPI® test (Method T245) for opacity compares the diffuse reflectancefrom a paper surface that is backed alternately by (a) a black cavity,from which essentially no light returns to the paper, and (b) a standardwhite tile surface having a reflectance of 89%. By contrast, theprinting opacity (TAPPI® Method T519) can be defined as the ratio ofreflectance from a paper sheet backed by a perfect black (either a blackcavity or a black tile), and from a sufficiently thick stack ofidentical sheets of paper.

Many problems related to opacity can be anticipated from anunderstanding of how light interacts with the structure of paper.Opacity usually is highly correlated to the efficiency of lightscattering by the paper material (except if there are large variationsin the color or in the amount of light-absorbing material). Highlight-scattering efficiency will be achieved if there is a highincidence of spaces within the paper that have dimensions greater thanat least a quarter of a wavelength of light. In rough terms, for thehighest light scattering, one wants the greatest number of interfacesbetween solid and air.

When applied to a fiber-containing layer, the present mineral-containinglayer(s) can substantially improve the opacity of the fiber-containinglayer when the fiber layer has an opacity as low as about 78 and up.Depending upon desired results, the mineral-containing layer can employa variety of mineral selections and can be both dispersed andnon-dispersed. Depending upon the nature and existing opacity of thefiber-containing layer, the fiber-containing layer can have improvedbrightness from about 5% to about 30%. For example, the fiber-containinglayer with an opacity of 79 could be improved to a brightness level ofabout 94 opaque.

Whiteness is an important cosmetic characteristic of a finished package.The CIE (Commission Internationale de l'Eclairage-InternationalCommission on Illumination) whiteness is a measure of whiteness is ameasurement of the light reflected by paper across the visible(daylight) spectrum. The CIE have set a standard of D65 illumination,which is a standard representation of outdoor daylight under which theamount of light reflected is measured. For a perfect reflectingnon-fluorescent white material, the CIE whiteness would be 100. Howevermost ‘white’ paper will have CIE whiteness measures of between 130 and170 due to the addition of Optical Brightening Agents (OB As), which aredesigned to reflect light from the non-visible range (mainlyultraviolet) back in the visible spectrum.

Depending upon desired CIE whiteness requirements for the finishedcomposite surface, the mineral-containing layer in the present compositestructures can employ a variety of mineral selections and be bothdispersed and non-dispersed within the overall mineral composite layer.Particles can vary in size, shape, and type. Depending upon the natureand existing CIE whiteness of the fiber-containing layer, thefiber-containing layer can have improved whiteness from about 5% toabout 80%. For example, the fiber-containing layer with a whiteness of79 could be improved to a brightness level of about 141 white.

Barrier performance in the area of moisture, oils, fatty acids, andwater are critical aspects of food, detergent, and other packagingapplications within the consumer packaging space. Because paper is arandomly felted layer of fiber, its structure has a varying degree ofporosity. Thus, the ability of fluids, both liquid and gaseous, topenetrate the structure of paper becomes highly significant to the useof paper.

Methods currently used in consumer packaging structures relating tobarrier performance include neat thermoplastic coatings applied insingle and multiple layers contacting the fiber surface. Also, a varietyof emulsion and waterborne polymer- and mineral-containing coatings canbe applied with or without using thermoplastics and at roomtemperatures. However, these methods are either costly or do not providedesired levels of barrier performance, most particularly at the point offracture or bending when cutting, shaping, and forming a packagingstructure. Further, heat scalability and fiber adhesion are othercritical aspects during the packaging manufacture and forming process.Finally, high quality printing surfaces are desirable, and existingmethods do not provide sufficient cosmetics at desired cost levels.

Extruded mineral-containing interspersed and non-interspersed compositelayers of the present embodiments demonstrate high barrier performancecharacteristics when substantially and continuously bonded tofiber-containing layers. The fiber-containing layers may include intheir composition or surface, but are not limited to, mineral andpolymeric sizings, surface treatments, coatings, and mineral fillers.Some advantages of the non-fiber content of the fiber containing layerinclude improved fiber layer printability, ink hold out, dynamic waterabsorption, water resistance, sheet gloss, whiteness, delta gloss, pickstrength, and surface smoothness. Often, mineral content containedwithin or upon one or more opposing surfaces of the fiber-containinglayer can include, but is not limited to, clay, calcined clay, orcombinations thereof. The minerals are frequently applied to the surfaceof the fiber-containing layer through a blade or air coating process.Common mineral binding methods include the use of protein systems suchas a mixture of vinyl acrylic/protein co-binders. Another non-limitingexample is tribinder systems, e.g. SB/Pvac/Protein. Further, pigmentssuch as TiO₂ can be included to improve whiteness characteristics. Thenature of the fiber layer's mineral and binder content can impact theselection of the non-interspersed and interspersed mineral-containinglayer characteristics when bonded substantially and continuously to oneor more sides of the fiber containing layer(s), which comprise part ofthe composite structure. Examples of non-fiber content in thefiber-containing layer include, but are not limited to, 50-95% of #1clay or #1 fine clay, 3-20% by part calcined clay, 3-40% by part TiO₂,2-45% vinyl acrylic, and from about 1% to about 35% protein binders,co-binders, or tri-binders.

Also, the fiber-containing layer surfaces can have from about 55% toabout 88% TAPPI® 452 surface brightness. The examples shown in Table 14,below, illustrate acceptable, but not limiting, fiber-containing layercharacteristics for substantially and continuously bonding to themineral-containing layer. Surface roughness values are based upon ParkerPrint Surf (μm) and Bendtsen (mis/min) per TAPPI® T-479 (moderatepressure), TAPPI®T-538, and TAPPI® 555 (print-surf method). Tearresistance per TAPPI® T-414 standards are expressed in millinewtons(mN). Surface brightness is expressed per TAPPI® 452. Burst strength isexpressed per TAPPI® 403 standards. Bursting strength is reported asburst ratio=bursting strength (lbs/in2)/basis weight (lbs/ream).Internal bond strength or interlayer strength of the fiber containinglayer is an important characteristic as represented by TAPPI® T-403 andT-569. Preferred fiber-containing layer internal strengths are, but arenot limited to, from about 125 J/m² to about 1150 J/m². Further,fiber-containing layer Z-direction tensile strength per TAPPI® T-541testing standard is from about 45-50 Nm/g to about 950 Nrn/g. Finally,preferred, but non-limiting, fiber-containing layer air resistance perTAPPI® 547 is from about Oto about 1500 mis/min, as represented by theBendsten method.

TABLE 14 Fiber-Containing Layer Characteristics Fiber Tear Burst WeighResistance Surface Strength (lbs/3 msf) g/m² (Mn) Roughness (kPa) 40-75 60-110  400-700 2.0-5.5 μm 140-300 >75 110-130  650-750 2.0-3.5 μm175-400 >115 180-190 1400-1900 100-2500 mls/min 175-475 >130 205-2151600-2200 100-2500 mls/min 250-675 >200 315-330 1900-3200 100-2500mls/min 500-950 >300 460-195  500-4000 100-2500 mls/min 700-1850

Table 15, below, displays finished composite board barrier performanceranges, but is not limited to, that of a composite structure having fromabout 20% to about 70% mineral-containing layer bonded to at least oneside of a fiber-containing layer. The mineral-containing layer can beeither a dispersed monolayer or non-interspersed coextrusion, forexample.

TABLE 15 Barrier Values of Formed Composite Structure Test MethodTAPPI ® T441 TAPPI ® T464 TAPPI ® T410 TAPPI ® T559 Test Name WVTR inCobb Water Tropical Mineral layer Absorption Conditions Wgt GreaseResistance g/m² Units 3M Kit Test# Sample 2 minute 30 minute g/100lb/1000 Coated Uncoated # Fiber Layer Cobb Cobb g/m² in² g/m² ft′ SideSide 1 Recycled  28 mil 0.22 — 23.4 1.51 *12 **1- Fiber caliper 2 Virgin.20 mil 0.40 0.00 15.2 0.98 32.3 4.12 12 1- Fiber caliper 3 Recycled .20mil 0.00 — 18.6 1.20 3.45 12 1- Fiber caliper 4 85-100% .20 mil 0.100.05 13.9 0.89 18.25 3.55 12 1- Recycled caliper Fiber 5 Virgin- .30 mil7.58 0.49 12 1- TMP caliper content 6 Clay coated .18 mil — 0.45 7.130.46 7.5 12 1- 1 side- caliper bleached 7 Fiber 2-side .18 mil 0.00 —9.31 0.60 6.44 12 1- bleached caliper 8 Fiber 1 .18 mil 0.50 0.11 37.72.43 11.33 12 1- side, caliper bleached 9 Virgin  16 mil 0.05 0.11 15.00.97 3.94 12 1- Kraft-clay caliper coated 10 Virgin .14 mil 0.00 0.1014.1 0.91 28.1 3.89 12 1- Kraft-clay thick coated 11 Clay coated .18 mil0.00 0.05 13.0 0.84 6.2 12 1- unbleached caliper kraft-100% Virgin 12Solid .18 mil 0.00 0.00 9.49 0.61 52.2 5.5 12 1- Unbleached caliperSulfate

Table 16, below, shows the barrier performance of a formed compositehaving a monolayer HD PE-PE mix with a density from about 0.925 gm/cm3to about 0.960 g/cm³ containing from about 36% to about 45% mineralcontent by weight.

TABLE 16 Barrier Values of a Formed Composite Structure, Interspersed(Mono), Mineral- Containing Layer Monolayer 40%-60% Mineral Content(HDPE-PE MIX) WVTR in Tropical Cobb Water Conditions 100° AbsorptionF./90% R.H. Mineral Layer Weight Unit Fiber type g/m² g/100 lb/1000Sample 2-min 30-min g/m² in² g/m² ft² Recycled 0.2 0.1 16.7 1.08 24.95.09 Recycled 0.0 0.0 9.7 0.63 49.6 7.4 Virgin Kraft 0.0 0.1 11.1 0.7232.8 6.73 Virgin Kraft 0.1 0.1 9.9 0.64 36.9 7.57 Virgin Kraft 0.0 0.18.7 0.56 36.2 7.42 Virgin Kraft 0.0 0.2 7.8 0.50 41.0 6.46 Virgin Kraft— — — — 26.1 5.35

Table 17, below, shows projected moisture barrier performance (MVTR,WVTR) for the present embodiments, comparing a coextrudedmineral-containing layer bonded to a surface of a fiber-containinglayer, the mineral-containing layer having both a monolayer and amultilayer (coextrusion) construction. The fiber-containing layer inTable 17 lists Klabin virgin kraft fiber. However, the data isapplicable to a range of both virgin and recycled fiber surfaces toinclude similar various weights and densities known in the art. MaximumMVTR via coextrusion is projected to be about the values in Table 25 inmineral-containing layers down to about 12 g/m² layer weight. The dataillustrates two different MVTR values. The first value is coextrusion.Coextrusion can provide superior results because of the flexibility toalter the type of polymers used per layer, density, branched or linearmolecular nature, as well as crystallinity, among others. Also, becauseof stress fracturing found in more monolayer constructions as a resultof bending, scoring, and processing, performance improvements usingcoextrusion are possible. The base layer in the coextrusion can bedenser and crystalline, for example, than the outer layer, which is moreamorphous and light density and more linear, thus not as vulnerable tostress fracture within the matrix, preventing percolation through thelayer. Other options for improving processing include additives to themineral-containing blend, which include, but are not limited to,elastomers.

TABLE 17 Barrier Attributes of Mineral-Containing Layer Bonded toFiber-Containing Layer Based for Interspersed (Monolayer) andNon-Interspersed (Coextruded) Composite Flat Samples Full Case MineralLayer Project Barrier Performance Table Pre-Score + Bed Post ScoreMineral Ethylene Co-Polymer Layer Ranges WVTR- Density Fiber Layer −Outer Layer Tropical WVTR (g/cm³) % Uncoated Mineral gm/m² gm/m² WVTRWeight Range Amorphous Box board 38-65% Day Variation Day VariationRanges 1.22-1.41 25%-65% 20 pt. 2+ layer 5 to 13 0.20 11 to 0.2 15 gsmKlabin coex 17 50 gsm 1.22-1.36 25-70% 20 pt. Monolayer 8 to 22 0.2 14to 0.2 15 gsm Klabin 25 50 gsm

In the present embodiments, label composites containing a mineralcontent layer within the structure can be used for forming labels foruse in graphics, printing, engraving, marking, lasering, cosmetic, waveblock, environmental the present embodiments can be bonded into thelabel structure and/or applied to the label destination surface usingboth extrusion and hot and cold application techniques. Embodiments ofthe present mineral-containing layer also provide hot tack and adhesiveproperties. Further advantages include blocking and surface frictionperformance having impact on label immersion, stability, and removalperformance in exposure temperature conditions from about 70° F. toabout 130° F. And yet additional mineral-containing layer advantagesinclude die cutting and stripping performance related in part tocoefficients of friction provided by mineral particles making contactwith opposing surfaces having densities from about 5%-120% variable fromthat of existing label layers or adhesive surfaces.

Pressure sensitive labels having one or more mineral-containing layersaccording to the present embodiments can be permanently or temporarilyadhered or bonded during pre- or post-application (to the labeldestination surface), with the mineral-containing layer making contactdirectly to the chosen destination surface. Adhesive layers can makecontact with one or more opposing surfaces of the mineral-containinglayer. Further, one or more adhesives could make contact with themineral-containing layer and the outer surface of the structure on whichthe label is applied, or the mineral-containing layer could comprise theouter surface of the label, with an adhesive backing on the opposingouter mineral containing layer surface that is either permanently ortemporarily directly bonded to the product or packaging surface in whichthe product is enclosed.

From to about 20% to about 40% mineral-containing layers in the presentembodiments can make contact with thermoplastic or non-thermoplasticwaterborne or emulsion carried polymer or starch-containing adhesivesand glues currently used in the art. Adhesives can permanently ortemporarily bond the present mineral-containing layer(s) to any of theouter or inner surfaces of the label structure itself, forming the labelstructure that may be applied with our without heat or pressure, but notlimited to, label destination surfaces having metal, polymer, glass,woven, wood, cellulose, lignin, nano-treated surfaces, paper coatings,woven, or non-woven content. Further, the label itself may contain allor in part the same materials as the destination surface. Labelstructures might also include, for example, mineral-containing layersused as preprinted or non-preprinted layers that are subsequentlyadhered to corrugated liners and shaped to form corrugated structures.

The present mineral-containing layer or layers make functional contactwith adhesives found in outer or inner label surfaces. The surfacesinclude label liners used for cold, wet, or dry strength labelapplications in calipers from about 0.75 mil to about 10 mil. Thefinished labels can be used in both roll-to-roll or singly appliedapplications with basis weights from about 10 lbs/3 msf to about 400lbs/3 msf. The mineral containing layer can be used as a layer or partof a pressure sensitive label having an MD-CD strength from about 4 to 9lbs per inch to about 1 to 15 lbs per inch, MD-CD tear strengths fromabout 60 grams to about 64 grams, and with MD-CD tear strengths fromabout 2 lbs to about 15 lbs per sheet.

One example of label adhesive is emulsion acrylics contacting themineral-containing layer with metals, polyesters, polymers, andglass-containing surfaces. The adhesive has loop tack from about 1.5 lbsto about 3.5 lbs and corresponding peel adhesion from about 0.5 to about4.0 lbs. Surface application temperatures are from a minimum of about−22° F. with service temperatures from about −70° F. to about 220° F.

The present mineral-containing layer(s) can functionally contact one ormore polymer or polyester containing label liner layers within the labelstructures, often but not limited to label roll stock across a web, withthe liner layer having calipers from about 0.50 mil to about 2.5 mil andMD-CD tensile strengths from about 15,000 psi to about 60,000 psi andfrom about 16,000 to about 55,000 psi.

The present mineral-containing layer(s) may be functionally bonded tointernal and external label surfaces and also have at least one of itssurfaces applied to the outer surface of the destination package orproduct for the purpose of labeling. Non-limiting adhesives that can beused for bonding the mineral-containing layer to the destination productor package surface can include polyesters with crystallization rates offrom about 40 to about 90 and for polycarbonates from about 45 to about90, having low to high heat resistance and thermo-plasticity as measuredat about 60° C.

Other adhesive characteristics between the mineral layer and othersurfaces within the label, or between the mineral-containing layer as anouter or inner label surface area bonded to the destination surface, mayinclude adhesives having, without limitation: a DOT-T Peel of 1 N ormore on Kraft paper as measured by ASTM 1876, a heat of fusion of 1-70Jig and molecular weight up to about 60,000, having one of moretackifiers including aliphatic hydrocarbon resins, aromatic modifiedaliphatic hydrocarbon resins, hydrogenated poly-cyclo-pentadiene resins,poly-cyclo-pentadiene resins, gum rosins, gum rosin esters,poly-terpenes, aromatic modified poly-terpenes, terpene phenolics,aromatic modified hydrogenated poly-cyclo-pentadiene resins,hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins,hydrogenated rosin esters, derivatives thereof, and/or combinationsthereof.

Other adhesive characteristics between at least one side of themineral-containing layer and other surfaces within the label, or betweenthe mineral-containing layer as an outer or inner label surface areabonded to the destination surface, may include, without limitation,adhesives having one or more waxes such as polar waxes, non-polar waxes,oxidize and non-oxidized Fischer-Tropsch waxes, hydroxy-stearamidewaxes, functionalized waxes, PP waxes, PE waxes, wax modifiers, andcombinations thereof. The adhesive additives may include plasticizers,oils, stabilizers, antioxidants, pigments, dyestuffs, polymericadditives, defoamers, preservatives, thickeners, rheology modifiers,humectants, fillers, and water. The adhesive may further contain asdesired aliphatic oils, white oils, combinations thereof, and/orderivatives thereof.

Additional functional bonding characteristics between themineral-containing layer and other surfaces within the label, or betweenthe mineral-containing layer as an outer or inner label surface areabonded to the destination surface, may include adhesives having, withoutlimitation, polymeric additives including homo poly-alpha-olefins,copolymers of alpha-olefins, copolymers and terpolymers of diolefins,elastomers, polyesters, block copolymers, ester copolymers, acrylatepolymers, alkyl acrylate polymers, and vinyl acetate polymers.

Other functional bonding characteristics between the mineral-containinglayer and other surfaces within the label, or between themineral-containing layer as an outer or inner label surface area bondedto the destination surface, may include non-hot melt adhesives having,without limitation, pH levels from about 6.5 to about 8.8, boilingpoints for non-hot melt at approximately 212 F, specific gravity fromabout 0.89 to about 1.61 g/cm³, solids content from about 20% to about85%, viscosities from about 70 mPa·s to about 150 mPa·s, and runningtemperatures up to 320 F.

FIG. 9 is a schematic side cross-sectional view of a multilayerpackaging composite material 20 according to the present embodiments.The illustrated embodiment includes a mineral-containing layer 22 havingan outer or heat-sealable surface 24. FIG. 9A is a detail view of theportion of FIG. 9 indicated by the circle 9A. As shown in FIG. 9A, aplurality of mineral particles 26 are interspersed within a bondingagent 28, which may be a thermoplastic. With reference to FIG. 9 , themineral-containing layer 22 may be substantially and continuously bondedto a first surface 30 of a fiber-containing layer 32. Anothermineral-containing layer 22 may be substantially and continuously bondedto a second surface 34 of the fiber-containing layer 32, the secondsurface 34 being opposite the first surface 30. With reference to FIG.9A, the fiber-containing layer 32 includes a plurality of fiberparticles 36 interspersed within a bonding agent 38, which may be athermoplastic. The thermoplastic bonding agent of either or both of themineral-containing layer 22 and the fiber-containing layer 32 maycomprise, for example and without limitation, polyolefin, polyester, orany other thermoplastic or polymer-containing resins.

The mineral-containing layer(s) 22 may include about 30% to about 65%minerals, and the minerals may comprise any of the minerals describedthroughout this specification and combinations thereof. Themineral-containing layer(s) 22 may be adhered to the fiber-containinglayer 32 through coextrusion, extrusion-lamination, or any othersuitable method or process. Extrusion-lamination may comprise aseparately applied adhesive between the mineral and fiber containinglayers. The composite material 20 illustrated in FIG. 9 mayadvantageously be used as a single or multiple corrugate liner(s) ormedium(s) within a single layered or multilayered corrugated structure.

FIG. 10 is a schematic side cross-sectional view of another multilayerpackaging composite material 40 according to the present embodiments.The illustrated embodiment includes a mineral-containing layer 22substantially and continuously bonded to the first surface 30 of afiber-containing layer 32. In contrast to the embodiment of FIG. 9 , inthe embodiment of FIG. 10 the second surface 34 of the fiber containinglayer 32 is not bonded to a mineral-containing layer 22.

FIG. 11 is a schematic side cross-sectional view of a mineral-containingmaterial according to the present embodiments. The illustratedembodiment includes a mineral-containing layer 22 having both the firstand second surfaces 30, 34 uncovered by a mineral-containing layer 22.

FIG. 12 is a schematic detail view of a pellet 42 of amineral-containing resin with mineral particles interspersed within abonding agent, according to the present embodiments. Pellets such asthat illustrated in FIG. 12 may be used in an extrusion process toadhere the mineral-containing layer 22 and the fiber-containing layer 32to one another. With reference to FIG. 12 , the mineral particles 26 areinterspersed within the bonding agent 28 within the pellet 42.

FIG. 13 is a schematic side cross-sectional view of another multilayerpackaging composite material according to the present embodiments. Theillustrated embodiment includes a first mineral-containing layer 22substantially and continuously bonded to the first surface 30 of afiber-containing layer 32. A second mineral-containing layer 44 issubstantially and continuously bonded to the second surface 34 of thefiber-containing layer 32. The second mineral-containing layer 44comprises three layers or plies of the first mineral-containing layer22. The first and second mineral-containing layers 22, 44 may be securedto the fiber-containing layer 32 through any of the processes describedherein, such as coextrusion, extrusion-lamination, etc., or through anyother process. The plies 22 of the second mineral-containing layer maybe secured to one 44 another through any of the processes describedherein, such as coextrusion, extrusion lamination, etc., or through anyother process. One or more of the plies 22 may comprise a mineralcontent and/or a bonding agent that is different from the mineralcontent and/or the bonding agent of another one or more of the plies 22.Further, the illustrated embodiment in which the secondmineral-containing layer 44 comprises three layers or plies 22 is onlyone example. In other embodiments the second mineral-containing layer 44may have any number of layers or plies 22, such as two layers or plies,four layers or plies, five layers or plies, etc. In yet furtherembodiments, the fiber-containing layer 32 may have a multilayermineral-containing layer 44 adhered to both the first 30 and second 34surfaces.

FIG. 14 is a schematic side cross-sectional view of another multilayerpackaging composite material 46 according to the present embodiments.The material 46 of FIG. 14 includes multiple layers of any of thematerial layers described herein, such as a first dual layer 48 and asecond dual layer 50 with a corrugated layer 52 therebetween.

The composite materials illustrated in the foregoing figures anddescribed above are well-suited for use as packaging materials, such asfor packages for containing one or more products. For example, andwithout limitation, such packages may comprise folding cartons and/orboxes. The package material has high performance heat sealcharacteristics, elevated barrier performance, is repulpable, andprovides excellent cosmetics and favorable economics. The presentcomposite materials can also be used as components, or layers, ofmultilayer packaging structures, such as corrugated boxes, and/or beused as a single-layer or multilayer corrugated liner or medium.

EXAMPLE 1 Detergent Barrier Box Using Coextrusion

A 38.5% by weight mineralized HPDE-PE resin containing additives wascompounded using finely wet ground CaCO₃ that was coated for dispersionwith an approximately 1.0-1.5 micron mean particle size, limestoneoriginating, CaCO₃ particles with incremental quartz and crystallinesilica content. The specific heat of the ground CaCO₃ particles was 0.21kcal/kg C. The HDPE had a compound was then coextruded using themineralized HD PE-PE composite layer as a base layer applied at 22 g/m²coating thickness and contacting the uncoated side 320 g/m² weightKlabin virgin paper surface having a TAPPI® T-441 Sheffield Smoothnessof 74, a 7.5% moisture content, and TAPPI® T 556 MD-CD Taber Stiffnessof 39.9 and 17.4, respectively. The minor layer or top facing, outer,polymer layer of the coextrusion was about 8 g/m² weight. The base layerbeing predominately crystalline using the top layer to provideadditional moisture barrier at box fracture from bend, scoring, andfolding joints. The extrusion processing condition melt temperature forthe base layer was approximately 580° F. with barrel temperatures fromzone one to zone six from about 405° F. to 580° F. The base layer dietemperature zone was approximately 575° F. to 580° F. The extruder diegap setting was within the range of 0.025″ to 0.030″. Unfilled Westlake®brand top neat PE layer processing was consistent with neat LDPE. Theextruder air gap was approximately 611-811, providing sufficient baselayer oxidation and excellent adhesion use gas pre-heat, but withoutozone or primer layers. Extrusion line speeds were within the range of150-300 m/min. across a 50″-60″ web width. Post-corona treatment wasused. Roll stock was checked in process quality control for adhesionusing “tape” testing and saturated for pin holing. Coat weight testingwas done consistently using lab instrumentation. Finished and coatedroll stock was rewound and sent for converting. Successful convertingand packaging article forming, e.g. folding cartons/boxes, were done upto eight months post-extrusion coating. During converting, the rollstock was run on high speed detergent box production lines at speeds upto 500 cartons per minute. The enclosed detergent was sensitive tomoisture exposure and was shipped in tropical moisture conditions. Glueseams and small, medium, and large carton sizes were successfully formedhaving sufficient fiber tear meeting standards with both roomtemperature and hot melt adhesives, including the manufacturer's seam.Moisture barrier testing was completed for large size sampling sizes,which included full converted and formed case samples having MVTRperformance of 13.91 g/m²/24 hrs with a minimum of 13.03 g/m²/24 hrs,with a standard deviation of 0.86. These results compared to 40 g/m2in-line primed and then applied aqueous PVDC coatings on the same Klabinboard having an average MVTR of 18.92 g/m²/24 hrs with a minimum of16.83 g/m²/24 hrs, a maximum of 20.89 g/m²/24 hrs with a standarddeviation of 2.00, and also compared to 20 micron thick BOPP primed androll-to-roll laminated on the same Klabin board having an average MVTRof 15.03 g/m²/24 hrs with a minimum of 13.20 g/m²/24 hrs, a maximum of16.64 g/m²/24 hrs with a standard deviation of 1.41.

EXAMPLE 2 Monolayer 40% Mineralized Barrier Coating

A 43.5% by weight mineralized PE resin containing additives wascompounded using finely ground and stearate coated 1.0-1.5 micron meanparticle sized, limestone-originating, CaCO₃ particles with incrementalquartz and crystalline silica content. The resin blend also had 5%titanium dioxide (TiO₂) for a total mineral content of 48.5% by weight.The ground CaCO₃ particles had a specific heat of 0.21 kcal/kg° C. ThePE had a density of 0.919 g/cm³ The PE bonding agent had a melt flowindex of 16 g/10 minutes. The finished and pelletized mineralizedcompound had an approximate density of 1.38 g/cm³ The compound was thenextruded using the mineralized PE and TiO₂ composite layer as a monolayer applied at 32 lbs/3 msf coating weight contacting the uncoatedside of Rock Term AngelCote® approximately 100% recycled fiberboard withnominal basis weight of 78 lbs/msf, with the paper surface having aTAPPI® T-441 Sheffield Smoothness of approximately 68-72, a 5% to 7.5%moisture content, and TAPPI® T 556 MD-CD Taber Stiffness g-cm of 320 and105, respectively. The extrusion processing condition melt temperaturewas approximately 585° F. with barrel temperatures from zone one to zonesix from about 400° F. to 585° F. The die temperature zones wereapproximately 575° F. to 585° F. The extruder die gap setting was withinthe range of 0.025″ to 0.030″. The extruder air gap was approximately6″-10″, providing excellent extrudate to fiber adhesion without a gaspre-heat, ozone, or primer layers. Extrusion line speeds were within therange of 150-400 feet per minute across an 80″-84″ web width.Post-corona treatment was used. Roll stock was quality control checkedin process for adhesion using “tape” testing and saturated for visualpin holing. Post-production coat weight testing was done consistentlyusing lab instrumentation. Finished and coated roll stock was rewoundand sent for converting. Successful converting and packaging forming wasdone up to three months post-extrusion coating. During converting theroll stock was run for use in high barrier MVR requirement frozenseafood box production lines at speeds up to 250 boxes per minute. Thefinished composite material was formed, bent, scored and machined atstandard production rates. The mineral-containing surface layer wasefficiently offset printed using standard industry inks and aqueouspress coatings. The mineral coating layer was highly opaque and improvedthe brightness of the base paper surface from about 59 bright to about76 bright. The mineral layer had a resident dyne level range of 44-48 asmeasured during post-production testing. Moisture barrier testing wascompleted for large size sampling sizes, which included full convertedand formed case samples having MVTR performance of 12 to 16 g/m²/24 hrs@ 100% humidity in tropical conditions with mineral composite layer coatweights from 14 lbs/3 ms to 16 lbs/3 msf.

The present embodiments provide a composite packaging structure havingmineral and fiber content that improve the material's printability, andmake the material environmentally friendly, attractive to consumers,capable of being manufactured at high speeds, and having lower materialcosts. The composite structure requires less polymer content thanexisting materials and provides improved internal and external adhesionand heat seal characteristics during packaging forming.

The composite structures described herein are well suited to be formedinto containers of various types. For example, FIG. 15 illustrates acontainer comprising a box 60. The box 60 may have many applications,such as, without limitation, retail and shipping. The box 60 may be inthe form of a cube or other parallelepiped that is sized to contain anitem for retail sale and/or shipping. The box 60 may be formed bypreparing the composite structure in the form of a pliable sheet, forexample by performing a milling step and/or other processing steps asdescribed above, cutting the structure into a desired shape, and thenfolding and/or creasing the sheet, either manually or by machine, suchas via an automated cartoning process, to form the finalthree-dimensional box shape. Abutting surfaces of the box 60 may besecured to one another using the various heat seal processes describedherein and/or other heat seal processes known in the art. In theembodiment shown in FIG. 15 , the composite structure forms the walls ofthe box 60, including a bottom wall 62, one or more side walls 64, aswell as a fold-over lid portion 66.

In other embodiments, the composite structures described herein may beformed into a container liner 70 for retail and/or shipping use, asshown in FIG. 16 . The liner 70 may be used to line a shipping or retailcontainer 72 to cushion and/or protect a product held in the container72, as well as to provide moisture resistance and deter infiltration ofrodents and other pests. The liner 70 formed of the composite structuremay be sufficiently flexible and pliable such that it is capable of atleast partially conforming to the shape of the container 72.

In other embodiments, the composite structures described herein may beformed into a shipping mailer 80, such as an envelope, which may be usedto ship documents and/or other items, as shown in FIG. 17 . Thecomposite structure may be used to form a part of or even all of themailer structure 80 and may be fabricated by using a series of folding,creasing, and/or adhesive/heat seal steps to prepare the desired mailershape.

In other embodiments, the composite structures described herein may beformed into a display tray 90 and/or other sales displays, as shown inFIG. 18 . For example, the composite structure may be cut, shaped,and/or folded into the shape of a display tray 90 capable of holding anddisplaying products for retail sale. The composite structure can bemolded by bending and/or folding, as well as via thermo- and/orvacuum-forming to form desired parts of the display 90.

Other non-limiting examples of applications for which the presentembodiments are well suited are described in one or more of thefollowing publications, each of which is incorporated herein byreference in its entirety: U.S. Patent Application Publication Nos.2009/0047499, 2009/0047511, and 2009/0142528.

The above description presents various embodiments of the presentdisclosure, and the manner and process of making and using them, in suchfull, clear, concise, and exact terms as to enable any person skilled inthe art to which it pertains to make and use the disclosed embodiments.The packaging materials and methods related thereto are, however,susceptible to modifications and alternate constructions from thatdiscussed above that are fully equivalent. Consequently, the packagingmaterials and methods are not limited to the particular embodimentsdisclosed. On the contrary, the packaging materials and methods coversall modifications and alternate constructions coming within the spiritand scope of the disclosed embodiments as generally expressed by thefollowing claims, which particularly point out and distinctly claim thesubject matter of the present disclosure.

What is claimed is:
 1. A composite barrier structure, comprising: one ormore barrier layers, wherein said one or more barrier layers compriseone to six coextruded non-interspersed layers, each layer of said one tosix coextruded non-interspersed layers is between 0% to 70% by weightmineral particles that are evenly dispersed in a thermoplastic bondingagent; wherein each of said coextruded non-interspersed layers of saidone to six coextruded non-interspersed layers has a total layer weightof about 2.5 lbs/3 msf to about 150 lbs/3 msf; wherein said mineralparticles comprise (i) a plurality of mineral nano-particles that are100 nanometers or less in size in at least one dimension and (ii) aplurality of ultrafine mineral nano-particles in at least one dimensionranging from 0.06 microns to 0.10 microns in size.
 2. The compositebarrier structure of claim 1, wherein said one or more barrier layershave a combined thickness in the range from about 0.5 mil to about 5mil; and wherein each layer of said one or more barrier layers has adensity from about 0.91 g/cm3 to about 1.55 g/cm3 or wherein said one ormore barrier layers have a combined layer weighted average density fromabout 0.91 g/cm3 to about 1.55 g/cm3.
 3. The composite barrier structureof claim 1, said one or more barrier layers further comprise one or moreof nano-fibrils, micro-fibrils, and nanofibril bundles, having lateraldimensions from about 0.4-30 nanometers (nm) to several microns, andhighly crystalline nano-whiskers from about 100 to 1000 nanometers. 4.The composite barrier structure of claim 1, wherein at least a portionof said mineral particles have a mean particle size in the range of 0.1microns to 10.0 microns.
 5. The composite barrier structure of claim 1,said composite barrier structure is an oxygen barrier.
 6. The compositebarrier structure of claim 1, wherein said thermoplastic bonding agenthas a crystallinity in the range of 60% to 85%.
 7. The composite barrierstructure of claim 1, wherein said thermoplastic bonding agent hasmolecular weights in the range of Mw 10,000 to Mw 100,000 and abranching index (g′) from 0.99 to 0.65 as measured at the Z-averagemolecular weight (Mz) of said thermoplastic bonding agent.
 8. Thecomposite barrier structure of claim 1, wherein said plurality ofmineral nano-particles are selected from the group of mineralsconsisting of: wollastonite (hydrated and non-hydrated); magnesiumsilicate; barium sulfate; barium ferrite; magnesium hydroxide; magnesiumcarbonate; aluminum trihydroxide; magnesium carbonate; natural silica orsand; cristobalite; diatomite; novaculite; quartz tripoli clay calcined;muscovite; nepheline-syenite; feldspar; calcium sulfate-gypsum; terraalba; selenite; domite; silicon mica; hydrated aluminum silicates; coke;montmorillonite (MMT); attapulgite (AT) carbon black; pecan nut flour;cellulose particles; wood flour; fly ash; starch; titanium dioxide(Ti02); barium carbonate; terra alba; selenite; nepheline-syenite;muscovite; pectolite; chrysotile; borates; sulfates; and precipitatedand ground calcium carbonate.
 9. The composite barrier structure ofclaim 1, wherein said plurality of mineral nano-particles are one ormore of: wollastonite (hydrated and non-hydrated); magnesium silicate;barium sulfate; barium ferrite; magnesium hydroxide; magnesiumcarbonate; aluminum trihydroxide; magnesium carbonate; natural silica orsand; cristobalite; diatomite; novaculite; quartz tripoli clay calcined;muscovite; nepheline-syenite; feldspar; calcium sulfate-gypsum; terraalba; selenite; domite; silicon mica; hydrated aluminum silicates; coke;montmorillonite (MMT); attapulgite (AT) carbon black; pecan nut flour;cellulose particles; wood flour; fly ash; starch; titanium dioxide(Ti02); barium carbonate; terra alba; selenite; nepheline-syenite;muscovite; pectolite; chrysotile; borates; sulfates; precipitated andground calcium carbonate; and combinations thereof.
 10. The compositebarrier structure of claim 1, wherein said plurality of ultrafinemineral nano-particles are selected from the group of mineralsconsisting of: wollastonite (hydrated and non-hydrated); magnesiumsilicate; barium sulfate; barium ferrite; magnesium hydroxide; magnesiumcarbonate; aluminum trihydroxide; magnesium carbonate; natural silica orsand; cristobalite; diatomite; novaculite; quartz tripoli clay calcined;muscovite; nepheline-syenite; feldspar; calcium sulfate-gypsum; terraalba; selenite; domite; silicon mica; hydrated aluminum silicates; coke;montmorillonite (MMT); attapulgite (AT) carbon black; pecan nut flour;cellulose particles; wood flour; fly ash; starch; titanium dioxide(Ti02); barium carbonate; terra alba; selenite; nepheline-syenite;muscovite; pectolite; chrysotile; borates; sulfates; and precipitatedand ground calcium carbonate.
 11. The composite barrier structure ofclaim 1, wherein said plurality of ultrafine mineral nano-particles areone or more of: wollastonite (hydrated and non-hydrated); magnesiumsilicate; barium sulfate; barium ferrite; magnesium hydroxide; magnesiumcarbonate; aluminum trihydroxide; magnesium carbonate; natural silica orsand; cristobalite; diatomite; novaculite; quartz tripoli clay calcined;muscovite; nepheline-syenite; feldspar; calcium sulfate-gypsum; terraalba; selenite; domite; silicon mica; hydrated aluminum silicates; coke;montmorillonite (MMT); attapulgite (AT) carbon black; pecan nut flour;cellulose particles; wood flour; fly ash; starch; titanium dioxide(Ti02); barium carbonate; terra alba; selenite; nepheline-syenite;muscovite; pectolite; chrysotile; borates; sulfates; precipitated andground calcium carbonate; and combinations thereof.
 12. The compositebarrier structure of claim 1, wherein said mineral particles areselected from the group of minerals consisting of clay and silica. 13.The composite barrier structure of claim 1, wherein said mineralparticles are one or more of clay and silica.
 14. The composite barrierstructure of claim 1, wherein said mineral particles are clay.
 15. Thecomposite barrier structure of claim 1, wherein said mineral particlesare silica.
 16. The composite barrier structure of claim 1, wherein saidmineral particles further comprise a nano-cellulose; wherein saidnano-cellulose has a crystalline content in the range of 40% to 70%. 17.The composite barrier structure of claim 16, wherein said crystallinecontent comprises one or more of nano-fibrils, micro-fibrils, andnanofibril bundles.
 18. The composite barrier structure of claim 16,wherein a first portion of said crystalline content has lateraldimensions in the range of 0.4 nanometers to 30.0 nanometers; wherein asecond portion of said crystalline content has lateral dimensions in therange of 1.0 micrometers to 10.0 micrometers; and wherein a highlycrystalline nano-whisker portion of said crystalline content has lateraldimensions in the range of 0.1 micrometers to 1.0 micrometers.
 19. Thecomposite barrier structure of claim 16, wherein a first portion of saidcrystalline content has widths in the range of 3.0 to 15.0 nanometers.20. The composite barrier structure of claim 16, wherein saidcrystalline content has charge densities in the range of 0.5 mEq/g(milliequivalent to grams) to 1.5 mEq/g (milliequivalent to grams). 21.The composite barrier structure of claim 16, wherein said nano-cellulosehas a stiffness in the range of 140 GPa to 220 GPa.
 22. The compositebarrier structure re of claim 16, wherein said nano-cellulose hastensile strength in the range of 400 Mpa to 600 Mpa.
 23. The compositebarrier structure of claim 1, wherein said one or more barrier layershave T410 weights from 5.5 g/m2 to 52.2 g/m2, T464 moisture barriervalues from 0.46 g/100 in2 to 37.7 g/100 in2, T441 Cobb 2-minute waterabsorption from 0.00 to 0.40, T441 30-minute water absorption from 0.00to 0.45, and a T559 grease resistance of 12.0.
 24. The composite barrierstructure of claim 1, wherein each of said barrier layers of said one ormore barrier layers has a thickness in the range from about 0.5 mil toabout 5 mil; and wherein each layer of said one or more barrier layershas a density from about 0.91 g/cm3 to about 1.55 g/cm3 or wherein saidone or more barrier layers have a combined layer weighted averagedensity from about 0.91 g/cm3 to about 1.55 g/cm3.